Concentrated Shampoo Dosage of Foam Designating Hair Conditioning Benefits

ABSTRACT

Described herein is a dosage of foam including from about 5 cm 3  to about 70 cm 3  of the foam. The foam includes from about 0.5 g to about 4 g of a detersive surfactant; from about 0.001 g to about 4 g propellant, a foam density of from about 0.05 g/cm 3  to about 0.35 g/cm 3 ; a bubble size distribution including an R 32  of from about 5 μm to about 100 μm; and a gloss unit measurement of from about 4 to about 40 GU. The propellant is selected from 1,3,3,3-tetrafluoroprop-1-ene, 1,1 difluoroethane, and mixtures thereof.

FIELD OF THE INVENTION

Described herein is a concentrated shampoo dosage of foam whichdesignates hair conditioning benefits.

BACKGROUND OF THE INVENTION

Foams for the hair care represent an attractive form to the consumers. Ashampoo product delivered via foam is readily spread on hair and enableshair cleansing without leaving significant residue on hair. The lowdensity of the foam necessitates a high surfactant composition in orderfor the consumer to receive the appropriate level of cleansing in arealistic product volume in one dose. The delivery of shampoo andconditioner products via foam is not common today. Thus, the appearanceof the delivered form must be delightful to the consumer and impact theperception of the desired product benefit. Based on the foregoing, thereis a need for concentrated shampoo products that are delivered as foamswith consumer preferred visual appearance properties.

Described herein are dosages of foam having a gloss unit measurementwhich provides a high consumer acceptance rating in terms of hairconditioning benefits based on a visual examination of dosages of foam.

SUMMARY OF THE INVENTION

Described herein is a dosage of foam comprising from about 5 cm³ toabout 70 cm³ of the foam, wherein the foam comprises: (a) from about 0.5g to about 4 g of a detersive surfactant by weight of the foam; (b) fromabout 0.001 g to about 4 g propellant by weight of the foam, wherein thepropellant is selected from the group consisting of hydrofluorocarbons(HFCs), hydrofluoroolefins (HFOs), and mixtures thereof; (c) a foamdensity of from about 0.05 g/cm³ to about 0.35 g/cm³; (d) a bubble sizedistribution comprising an R₃₂ of from about 5 μm to about 100 μm; and(e) a gloss unit measurement of from about 4 to about 40 GU.

Also described herein is a dosage of foam comprising from about 5 cm³ toabout 70 cm³ of the foam, wherein the foam comprises: (a) from about 0.5g to about 4 g of a detersive surfactant by weight of the foam; (b) fromabout 0.001 g to about 4 g propellant by weight of the foam, wherein thepropellant is selected from the group consisting of hydrofluorocarbons(HFCs), hydrofluoroolefins (HFOs), and mixtures thereof; (c) a foamdensity of from about 0.05 g/cm³ to about 0.35 g/cm³; (d) from about0.00005 g to about 0.25 g of a cationic deposition polymer by weight ofthe foam; (e) a bubble size distribution comprising an R₃₂ of from about5 μm to about 100 μm; and (f) a gloss unit measurement of from about 4to about 40 GU.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing outand distinctly claiming the invention, it is believed that the presentinvention will be better understood from the following description.

As used herein, the term “fluid” includes liquids and gels.

As used herein, the articles including “a” and “an” when used in aclaim, are understood to mean one or more of what is claimed ordescribed.

As used herein, “comprising” means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of”.

As used herein, “mixtures” is meant to include a simple combination ofmaterials and any compounds that may result from their combination.

As used herein, “molecular weight” or “Molecular weight” refers to theweight average molecular weight unless otherwise stated. Molecularweight of polymers may be measured using industry standard method, gelpermeation chromatography (“GPC”).

As used herein, the terms “include,” “includes,” and “including,” aremeant to be non-limiting and are understood to mean “comprise,”“comprises,” and “comprising,” respectively.

As used herein, the term “viscosity reducing agent” can mean organiccompounds having a molecular weight of from about 100 to about 300daltons, alternatively from about 125 daltons to about 300 daltons.Additionally, the viscosity reducing agents may have a water solubilityat between 23 and 25 degrees Celsius of from about 900 to 50,000 mg/L.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include carriers or by-products thatmay be included in commercially available materials.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Dosage of Foam

The dosage of foam can have a volume of from about 5 cm³ to about 70cm³, alternatively from about 10 cm³ to about 70 cm³, alternatively fromabout 15 cm³ to about 70 cm³, alternatively from about 20 cm³ to about70 cm³, alternatively from about 30 cm³ to about 70 cm³, alternativelyfrom about 5 cm³ to about 40 cm³, alternatively from about 7.5 cm³ toabout 30 cm³, alternatively from about 10 cm³ to about 90 cm³,alternatively from about 5 cm³ to about 150 cm³, alternatively fromabout 5 cm³ to about 30 cm³, alternatively from about 2.5 cm³ to about40 cm³, alternatively from about 10 cm³ to about 50 cm³, alternativelyfrom about 2.5 cm³ to about 40 cm³, alternatively from about 15 cm³ toabout 90 cm³, alternatively from about 15 cm³ to about 150 cm³,alternatively from about 15 cm³ to about 30 cm³, alternatively fromabout 15 cm³ to about 40 cm³, alternatively from about 15 cm³ to about50 cm³, alternatively from about 20 cm³ to about 60 cm³, alternativelyfrom about 20 cm³ to about 50 cm³, and alternatively from about 15 cm³to about 40 cm³.

The dosage of foam can comprise from about 0.5 g to about 12 g,alternatively from about 0.5 g to about 8 g, alternatively from about0.5 g to about 4 g, alternatively from about 0.5 g to about 3 g,alternatively from about 0.5 g to about 1.75 g, alternatively from about1 g to about 1.25 g, alternatively from about 1 g to about 8 g,alternatively from about 1.25 g to about 4 g, alternatively from about1.5 g to about 3 g, alternatively from about 1.25 g to about 2.0 g,alternatively from about 1 g to about 1.75 g, alternatively from about 1g to about 1.25 g of a detersive surfactant by weight of the foam.

The dosage of foam can also comprise from about 0.0001 g to about 5 g,alternatively from about 0.001 g to about 5 g, alternatively from about0.001 g to about 4 g, alternatively from about 0.01 g to about 4 g,alternatively from about 0.05 g to about 3 g, alternatively from about0.1 to about 2 g, alternatively from about 0.075 g to about 2 gpropellant by weight of the foam, alternatively from about 0.05 g toabout 1 g, and alternatively from about 0.05 g to about 0.5 g.

The dosage of foam can also have a foam density of from about 0.05 g/cm³to about 0.35 g/cm³, alternatively from about 0.08 g/cm³ to about 0.25g/cm³, alternatively from about 0.08 g/cm³ to about 0.2 g/cm³,alternatively from about 0.08 g/cm³ to about 0.18 g/cm³, alternativelyfrom about 0.08 g/cm³ to about 0.15 g/cm³, alternatively from about 0.08g/cm³ to about 0.12 g/cm³; alternatively from about 0.1 g/cm³ to about0.12 g/cm³, alternatively from about 0.12 g/cm³ to about 0.2 g/cm³, oralternatively from about 0.15 g/cm³ to about 0.2 g/cm³.

The dosage of foam can also have a bubble size distribution comprisingan R₃₂ of from about 5 μm to about 100 μm, alternatively from about 10μm to about 60 μm, alternatively from about 20 μm to about 50 μm; andalternatively from about 25 μm to about 40 μm.

The dosage of foam can have a yield point of from about 5 Pa 10 about100 Pa, alternatively from about 15 Pa to about 100 Pa, alternativelyfrom about 20 Pa to about 100 Pa, alternatively from about 25 Pa toabout 100 Pa, alternatively from about 38 Pa to about 100 Paalternatively from about 4 Pa to about 39 Pa, alternatively from about 5Pa to about 20 Pa, and alternatively from about 6 Pa to about 19 Pa.

The dosage of foam can have from about 0.00005 g to about 0.25 g of acationic deposition polymer by weight of the foam.

The dosage of foam can have a gloss unit measurement of from about 4 GUto about 150 GU, alternatively from about 4 GU to about 100 GU,alternatively from about 4 GU to about 75 GU, alternatively from about 4GU to about 40 GU, alternatively from about 5 GU to about 30 GU,alternatively from about 5 GU to about 20 GU, alternatively from about 5GU to about 15 GU, alternatively from about 20 GU to about 100 GU,alternatively from about 40 GU to about 75 GU, alternatively from about30 GU to about 40 GU, alternatively from about 10 GU to about 30 GU,alternatively from about 5 GU to about 10 GU, and alternatively fromabout 40 GU to about 150 GU.

Hair Care Compositions

Also described herein are hair care compositions that can deliver thedosages of foam described herein when actuated via an aerosol dispenser.

Detersive Surfactant

The hair care compositions described herein may comprise greater thanabout 20% by weight of a surfactant system which provides cleaningperformance to the composition. The surfactant system comprises ananionic surfactant and/or a combination of anionic surfactants, with aco-surfactant selected from the group consisting of amphoteric,zwitterionic, nonionic and mixtures thereof. Various examples anddescriptions of detersive surfactants are set forth in U.S. Pat. No.8,440,605; U.S. Patent Application Publication No. 2009/155383; and U.S.Patent Application Publication No. 2009/0221463, which are incorporatedherein by reference in their entirety.

The hair care composition may comprise from about 10% to about 40%, fromabout 15% to about 36%, from about 18% to about 32%, from about 20% toabout 30%, and/or from about 22% to about 28% by weight of one or moreanionic surfactants.

Anionic surfactants suitable for use herein include alkyl sulfates andalkyl ether sulfates of the formula ROSO₃M and RO(C₂H₄O)_(x)SO₃M,wherein R is alkyl or alkenyl of from about 8 to about 18 carbon atoms,x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium,potassium, and triethanolamine cation or salts of the divalent magnesiumion with two anionic surfactant anions. The alkyl ether sulfates may bemade as condensation products of ethylene oxide and monohydric alcoholshaving from about 8 to about 24 carbon atoms. The alcohols can bederived from fats such as coconut oil, palm oil, palm kernel oil, ortallow, or can be synthetic.

The composition of the present invention can also include anionicsurfactants selected from the group consisting of:

a) R₁ O(CH₂CHR₃₀)_(y) SO₃M;

b) CH₃ (CH₂)_(z) CHR₂ CH₂ O(CH₂ CHR₃O)_(y) SO₃M; and

c) mixtures thereof,

where R₁ represents CH₃ (CH₂)₁₀, R₂ represents H or a hydrocarbonradical comprising 1 to 4 carbon atoms such that the sum of the carbonatoms in z and R₂ is 8, R₃ is H or CH₃, y is 0 to 7, the average valueof y is about 1 when y is not zero (0), and M is a monovalent ordivalent, positively-charged cation.

Anionic surfactants suitable for use in the compositions are the alkyland alkyl ether sulfates. Other suitable anionic surfactants are thewater-soluble salts of organic, sulfuric acid reaction products. Stillother suitable anionic surfactants are the reaction products of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Other similar anionic surfactants are described in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated hereinby reference in their entirety.

Examples of additional anionic surfactants suitable for use hereininclude, but are not limited to, ammonium lauryl sulfate, ammoniumlaureth sulfate, triethylamine lauryl sulfate, triethylamine laurethsulfate, triethanolamine lauryl sulfate, triethanolamine laurethsulfate, monoethanolamine lauryl sulfate, monoethanolamine laurethsulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate,lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodiumlaureth sulfate, potassium laureth sulfate, sodium lauryl sarcosinate,sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammoniumcocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodiumlauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate,monoethanolamine cocoyl sulfate, sodium trideceth-1 sulfate, sulfate,sodium trideceth-2 sulfate, sulfate, sodium trideceth-3 sulfate, sodiumtridecyl sulfate, sodium methyl lauroyl taurate, sodium undecyl sulfate,sodium decyl sulfate, sodium methyl cocoyl taurate, sodium lauroylisethionate, sodium cocoyl isethionate, sodium laurethsulfosuccinate,sodium laurylsulfosuccinate, sodium tridecyl benzene sulfonate, sodiumdodecyl benzene sulfonate, and mixtures thereof.

Some non-limiting examples of anionic surfactants are:

Alkyl Sulfates:

where R is C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated)or mixtures thereof and M⁺ is monovalent cation. Examples include Sodiumlauryl sulfate (where R is C₁₂ alkyl and M⁺ is Na⁺), ammonium laurylsulfate (where R is C₁₂ alkyl and M⁺ is NH₃ ⁺), and sodium coco-sulfate(where R is coconut alkyl and M⁺ is Na⁺);

Alkyl Ether Sulfates:

where R is C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated)or mixtures thereof, n=1-12, and M⁺ is monovalent cation. Examplesinclude sodium laureth sulfate (where R is C₁₂ alkyl and M⁺ is Na⁺,n=1-3), ammonium laureth sulfate (where R is C₁₂ alkyl, M⁺ is NH₃ ⁺,n=1-3), and Sodium trideceth sulfate (where R is C₁₃ alkyl, M⁺ is Na⁺,and n=1-4);

Alkyl Glyceryl Ether Sulfonates:

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Sodium CocoglycerylEther Sulfonate (R=coco alkyl, M⁺=Na⁺);Alpha olefin sulfonates prepared by sulfonation of long chain alphaolefins. Alpha olefin sulfonates consist of mixtures of alkenesulfonates:

where R=C₈-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation;

Hydroxyalkyl Sulfonates:

where R=C₄-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation.Examples include Sodium C12-14 Olefin Sulfonate (R=C₈-C₁₀ alkyl, M⁺=Na⁺)and Sodium C 14-16 Olefin Sulfonate (R=C₁₀-C₁₂ alkyl, M⁺=Na⁺).

The composition can also include anionic alkyl sulfates and alkyl ethersulfate surfactants having branched alkyl chains which are synthesizedfrom C8 to C18 branched alcohols which may be selected from the groupconsisting of: Guerbet alcohols, aldol condensation derived alcohols,oxo alcohols and mixtures thereof. Non-limiting examples of the 2-alkylbranched alcohols include oxo alcohols such as 2-methyl-1-undecanol,2-ethyl-1-decanol, 2-propyl-1-nonanol, 2-butyl 1-octanol,2-methyl-1-dodecanol, 2-ethyl-1-undecanol, 2-propyl-1-decanol,2-butyl-1-nonanol, 2-pentyl-1-octanol, 2-pentyl-1-heptanol, and thosesold under the tradenames LIAL® (Sasol), ISALCHEM® (Sasol), and NEODOL®(Shell), and Guerbet and aldol condensation derived alcohols such as2-ethyl-1-hexanol, 2-propyl-1-butanol, 2-butyl-1-octanol,2-butyl-1-decanol, 2-pentyl-1-nonanol, 2-hexyl-1-octanol,2-hexyl-1-decanol and those sold under the tradename ISOFOL® (Sasol) orsold as alcohol ethoxylates and alkoxylates under the tradenamesLUTENSOL XP® (BASF) and LUTENSOL XL® (BASF).

The anionic alkyl sulfates and alkyl ether sulfates may also includethose synthesized from C8 to C18 branched alcohols derived from butyleneor propylene which are sold under the trade names EXXAL™ (Exxon) andMarlipal® (Sasol). This includes anionic surfactants of the subclass ofsodium trideceth-n sulfates (STnS), where n is between about 0.5 andabout 3.5. Exemplary surfactants of this subclass are sodium trideceth-2sulfates and sodium trideceth-3 sulfates. The composition of the presentinvention can also include sodium tridecyl sulfate.

The hair care composition may comprise a co-surfactant. Theco-surfactant can be selected from the group consisting of amphotericsurfactant, zwitterionic surfactant, non-inonic surfactant and mixturesthereof. The co-surfactant can include, but is not limited to,lauramidopropyl betaine, cocoamidopropyl betaine, laurylhydroxysultaine, sodium lauroamphoacetate, coco monoethanolamide andmixtures thereof.

The hair care composition comprises from about 1% to about 15%, fromabout 2% to about 12%, from about 3% to about 10%, from about 4% toabout 8% by weight of one or more co-surfactants selected from the groupconsisting of amphoteric surfactant, zwitterionic surfactant, non-inonicsurfactant and mixtures thereof.

Suitable amphoteric or zwitterionic surfactants for use in the hair carecomposition herein include those which are known for use in shampoo orother hair care cleansing. Non limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. Nos.5,104,646 and 5,106,609, which are incorporated herein by reference intheir entirety.

Amphoteric co-surfactants suitable for use in the composition includethose surfactants described as derivatives of aliphatic secondary andtertiary amines in which the aliphatic radical can be straight orbranched chain and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionic groupsuch as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Suitableamphoteric surfactant include, but are not limited to, those selectedfrom the group consisting of: sodium cocaminopropionate, sodiumcocaminodipropionate, sodium cocoamphoacetate, sodiumcocoamphohydroxypropylsulfonate, sodium cocoamphopropionate, sodiumcornamphopropionate, sodium lauraminopropionate, sodiumlauroamphoacetate, sodium lauroamphohydroxypropylsulfonate, sodiumlauroamphopropionate, sodium cornamphopropionate, sodiumlauriminodipropionate, ammonium cocaminopropionate, ammoniumcocaminodipropionate, ammonium cocoamphoacetate, ammoniumcocoamphohydroxypropylsulfonate, ammonium cocoamphopropionate, ammoniumcornamphopropionate, ammonium lauraminopropionate, ammoniumlauroamphoacetate, ammonium lauroamphohydroxypropylsulfonate, ammoniumlauroamphopropionate, ammonium cornamphopropionate, ammoniumlauriminodipropionate, triethanonlamine cocaminopropionate,triethanonlamine cocaminodipropionate, triethanonlaminecocoamphoacetate, triethanonlamine cocoamphohydroxypropylsulfonate,triethanonlamine cocoamphopropionate, triethanonlaminecornamphopropionate, triethanonlamine lauraminopropionate,triethanonlamine lauroamphoacetate, triethanonlaminelauroamphohydroxypropylsulfonate, triethanonlamine lauroamphopropionate,triethanonlamine cornamphopropionate, triethanonlaminelauriminodipropionate, cocoamphodipropionic acid, disodiumcaproamphodiacetate, disodium caproamphoadipropionate, disodiumcapryloamphodiacetate, disodium capryloamphodipriopionate, disodiumcocoamphocarboxyethylhydroxypropylsulfonate, disodiumcocoamphodiacetate, disodium cocoamphodipropionate, disodiumdicarboxyethylcocopropylenediamine, disodium laureth-5carboxyamphodiacetate, disodium lauriminodipropionate, disodiumlauroamphodiacetate, disodium lauroamphodipropionate, disodiumoleoamphodipropionate, disodium PPG-2-isodecethyl-7carboxyamphodiacetate, lauraminopropionic acid, lauroamphodipropionicacid, lauryl aminopropylglycine, lauryl diethylenediaminoglycine, andmixtures thereof

The amphoteric co-surfactant can be a surfactant according to thefollowing structure:

wherein R12 is a C-linked monovalent substituent selected from the groupconsisting of substituted alkyl systems comprising 9 to 15 carbon atoms,unsubstituted alkyl systems comprising 9 to 15 carbon atoms, straightalkyl systems comprising 9 to 15 carbon atoms, branched alkyl systemscomprising 9 to 15 carbon atoms, and unsaturated alkyl systemscomprising 9 to 15 carbon atoms; R13, R14, and R15 are eachindependently selected from the group consisting of C-linked divalentstraight alkyl systems comprising 1 to 3 carbon atoms, and C-linkeddivalent branched alkyl systems comprising 1 to 3 carbon atoms; and M+is a monovalent counterion selected from the group consisting of sodium,ammonium and protonated triethanolamine. In an embodiment, theamphoteric surfactant is selected from the group consisting of: sodiumcocoamphoacetate, sodium cocoamphodiacetate, sodium lauroamphoacetate,sodium lauroamphodiacetate, ammonium lauroamphoacetate, ammoniumcocoamphoacetate, triethanolamine lauroamphoacetate, triethanolaminecocoamphoacetate, and mixtures thereof.

The composition may comprises a zwitterionic co-surfactant, wherein thezwitterionic surfactant is a derivative of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight or branched chain, and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic group such as carboxy, sulfonate, sulfate,phosphate or phosphonate. The zwitterionic surfactant can be selectedfrom the group consisting of: cocamidoethyl betaine, cocamidopropylamineoxide, cocamidopropyl betaine, cocamidopropyl dimethylaminohydroxypropylhydrolyzed collagen, cocamidopropyldimonium hydroxypropyl hydrolyzedcollagen, cocamidopropyl hydroxysultaine, cocobetaineamidoamphopropionate, coco-betaine, coco-hydroxysultaine, coco/oleamidopropylbetaine, coco-sultaine, lauramidopropyl betaine, lauryl betaine, laurylhydroxysultaine, lauryl sultaine, and mixtures thereof. A suitablezwitterionic surfactant is lauryl hydroxysultaine. The zwitterionicsurfactant can be selected from the group consisting of: laurylhydroxysultaine, cocamidopropyl hydroxysultaine, coco-betaine,coco-hydroxysultaine, coco-sultaine, lauryl betaine, lauryl sultaine,and mixtures thereof.

The co-surfactant can be a zwitterionic surfactant, wherein thezwitterionic surfactant is selected from the group consisting of: laurylhydroxysultaine, cocamidopropyl hydroxysultaine, coco-betaine,coco-hydroxysultaine, coco-sultaine, lauryl betaine, lauryl sultaine,and mixtures thereof.

The co-surfactant can be a non-ionic surfactant selected from the groupconsisting of: Cocamide, Cocamide Methyl MEA, Cocamide DEA, CocamideMEA, Cocamide MIPA, Lauramide DEA, Lauramide MEA, Lauramide MIPA,Myristamide DEA, Myristamide MEA, PEG-20 Cocamide MEA, PEG-2 Cocamide,PEG-3 Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6 Cocamide, PEG-7Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3 Oleamide, PPG-2Cocamide, PPG-2 Hydroxyethyl Cocamide, and mixtures thereof.

Suitable nonionic surfactants for use include those described inMcCutcheion's Detergents and Emulsifiers, North American edition (1986),Allured Publishing Corp., and McCutcheion's Functional Materials, NorthAmerican edition (1992). Suitable nonionic surfactants for use in thehair care compositions include, but are not limited to,polyoxyethylenated alkyl phenols, polyoxyethylenated alcohols,polyoxyethylenated polyoxypropylene glycols, glyceryl esters of alkanoicacids, polyglyceryl esters of alkanoic acids, propylene glycol esters ofalkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylenatedsorbitor esters of alkanoic acids, polyoxyethylene glycol esters ofalkanoic acids, polyoxyethylenated alkanoic acids, alkanolamides,N-alkylpyrrolidones, alkyl glycosides, alkyl polyglucosides, alkylamineoxides, and polyoxyethylenated silicones.

Representative polyoxyethylenated alcohols include alkyl chains rangingin the C9-C16 range and having from about 1 to about 110 alkoxy groupsincluding, but not limited to, laureth-3, laureth-23, ceteth-10,steareth-10, steareth-100, beheneth-10, and commercially available fromShell Chemicals, Houston, Tex. under the trade names Neodol® 91, Neodol®23, Neodol® 25, Neodol® 45, Neodol® 135, Neodo®l 67, Neodol® PC 100,Neodol® PC 200, Neodol® PC 600, and mixtures thereof.

Also available commercially are the polyoxyethylene fatty ethersavailable commercially under the Brij® trade name from Uniqema,Wilmington, Del., including, but not limited to, Brij® 30, Brij® 35,Brij® 52, Brij® 56, Brij® 58, Brij® 72, Brij® 76, Brij® 78, Brij® 93,Brij® 97, Brij® 98, Brij® 721 and mixtures thereof.

Suitable alkyl glycosides and alkyl polyglucosides can be represented bythe formula (S)n-O—R wherein S is a sugar moiety such as glucose,fructose, mannose, galactose, and the like; n is an integer of fromabout 1 to about 1000, and R is a C8-C30 alkyl group. Examples of longchain alcohols from which the alkyl group can be derived include decylalcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearylalcohol, oleyl alcohol, and the like. Examples of these surfactantsinclude alkyl polyglucosides wherein S is a glucose moiety, R is a C8-20alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside and lauryl polyglucoside available under trade names APG®325 CS, APG® 600 CS and APG® 625 CS) from Cognis, Ambler, Pa. Alsouseful herein are sucrose ester surfactants such as sucrose cocoate andsucrose laurate and alkyl polyglucosides available under trade namesTriton™ BG-10 and Triton™ CG-110 from The Dow Chemical Company, Houston,Tex.

Other nonionic surfactants suitable for use are glyceryl esters andpolyglyceryl esters, including but not limited to, glyceryl monoesters,glyceryl monoesters of C12-22 saturated, unsaturated and branched chainfatty acids such as glyceryl oleate, glyceryl monostearate, glycerylmonopalmitate, glyceryl monobehenate, and mixtures thereof, andpolyglyceryl esters of C12-22 saturated, unsaturated and branched chainfatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3 oleate,polyglyceryl-2-sesquioleate, triglyceryl diisostearate, diglycerylmonooleate, tetraglyceryl monooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters. Sorbitanesters of C12-22 saturated, unsaturated, and branched chain fatty acidsare useful herein. These sorbitan esters usually comprise mixtures ofmono-, di-, tri-, etc. esters. Representative examples of suitablesorbitan esters include sorbitan monolaurate (SPAN® 20), sorbitanmonopalmitate (SPAN® 40), sorbitan monostearate (SPAN® 60), sorbitantristearate (SPAN® 65), sorbitan monooleate (SPAN® 80), sorbitantrioleate (SPAN® 85), and sorbitan isostearate.

Also suitable for use herein are alkoxylated derivatives of sorbitanesters including, but not limited to, polyoxyethylene (20) sorbitanmonolaurate (Tween® 20), polyoxyethylene (20) sorbitan monopalmitate(Tween® 40), polyoxyethylene (20) sorbitan monostearate (Tween® 60),polyoxyethylene (20) sorbitan monooleate (Tween® 80), polyoxyethylene(4) sorbitan monolaurate (Tween® 21), polyoxyethylene (4) sorbitanmonostearate (Tween® 61), polyoxyethylene (5) sorbitan monooleate(Tween® 81), and mixtures thereof, all available from Uniqema.

Also suitable for use herein are alkylphenol ethoxylates including, butnot limited to, nonylphenol ethoxylates (Tergitol™ NP-4, NP-6, NP-7,NP-8, NP-9, NP-10, NP-11, NP-12, NP-13, NP-15, NP-30, NP-40, NP-50,NP-55, NP-70 available from The Dow Chemical Company, Houston, Tex.) andoctylphenol ethoxylates (Triton™ X-15, X-35, X-45, X-114, X-100, X-102,X-165, X-305, X-405, X-705 available from The Dow Chemical Company,Houston, Tx).

Also suitable for use herein are alkanolamides including cocamidemonoethanolamine (CMEA) and tertiary alkylamine oxides includinglauramine oxide and cocamine oxide.

Nonionic surfactants useful herein have an HLB (hydrophile-lipophilebalance) of at least 8, in one embodiment greater than 10, and inanother embodiment greater than 12. The HLB represents the balancebetween the hydrophilic and lipophilic moieties in a surfactant moleculeand is commonly used as a method of classification. The HLB values forcommonly-used surfactants are readily available in the literature (e.g.,HLB Index in McCutcheon's Emulsifiers and Detergents, MC Publishing Co.,2004).

Non limiting examples of other anionic, zwitterionic, amphoteric, andnon-ionic additional surfactants suitable for use in the hair carecomposition are described in McCutcheon's, Emulsifiers and Detergents,1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos.3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporatedherein by reference in their entirety.

The shampoo composition can comprise of 20-45 wt % detersive surfactant,from which 0-10 wt % is amphoteric surfactant, 2-25% is a sulfate havinga branched alkyl carbon chain containing from C12 to C16 carbon atoms,5-30 wt % is a sulfate having a linear alkyl carbon chain containingfrom C12 to C16 carbon atoms, a water-miscible solvent from about 2 wt %to about 8 wt %, and water carrier from about 40 wt % to about 80 wt %,wherein the ratio of linear anionic surfactant:Branched anionicsurfactant is from about 0.4 to about 5.

The shampoo composition can comprise of 20-45 wt % detersive surfactant,from which 0-10 wt % is amphoteric surfactant, 6-30 wt % is a sulfatehaving a branched alkyl carbon chain containing from C12 to C16 carbonatoms, 0-20 wt % is a sulfate having a linear alkyl carbon chaincontaining from C12 to C16 carbon atoms, a water-miscible solvent fromabout 2 wt % to about 10 wt %, and water carrier from about 40 wt % toabout 80 wt %, wherein the weight ratio of (Linear anionicsurfactant/Branched anionic surfactant)/Miscible solvent is higher thanabout 0.2, and wherein the weight ratio of Branched anionicsurfactant/Miscible solvent is higher than 5.

The shampoo composition can comprise of 5-45 wt % detersive surfactant,from which 5-35 wt % is anionic detersive surfactant, a water-misciblesolvent from about 1 wt % to about 20 wt %, a hydrofluoro olefin foamingagent from about 3 wt % or higher, and water carrier from about 20 wt %to about 90 wt %, wherein the weight ratio of the foaming agent toWater-miscible solvent is lower than about 3.

The shampoo composition can comprise of 20-45 wt % detersive surfactant,from which 10-40 wt % is anionic detersive surfactant, 1-15 wt % of oneor more co-surfactants selected from the group consisting of amphoteric,zwitterionic, nonionic and mixtures thereof; wherein about 1% or moreare zwitterionic surfactants which possess a hydroxyl group in theirmolecular structure, from about 0.1% to about 35% by weight of one ormore viscosity reducing agents, from about 0.05% to about 1% by weightof one or more cationic polymers with a weight average molecular weightof less than about 1,000,000 g/mol.

The shampoo composition can comprise of 20-45 wt % detersive surfactant,from which 10-40 wt % is anionic detersive surfactant, 1-15 wt % of oneor more co-surfactants selected from the group consisting of laurylhydroxysultaine, coco-hydroxysultaine, sodium lauroamphoacetate, sodiumcocoamphoacetate, sodium lauroamphopropionate, sodiumcocoamphopropionate, and mixture thereof, from about 0.1% to about 35%by weight of one or more viscosity reducing agents, from about 0.05% toabout 1% by weight of one or more cationic polymers with a weightaverage molecular weight of less than about 1,000,000 g/mol.

Viscosity Reducing Agents

The hair care composition described herein may comprise from about 0.5%to about 15%, alternatively from about 0.75% to about 10.0%,alternatively from about 1% to about 7.5%, alternatively from about1.25% to about 5.0%, and alternatively from about 1.5% to about 3.5% ofa viscosity reducing agent, by weight of the hair care composition.Non-limiting examples of suitable viscosity reducing agents includewater miscible solvents, hydrotropes, Class A materials, Class Bmaterials, silicone polyethers, and mixtures thereof.

The hair care composition described herein may have a liquid phaseviscosity of from about 8 centipoise to about 15,000 centipoise,alternatively from about 9 centipoise to about 12,000 centipoise,alternatively from about 10 centipoise to about 11,000 centipoise,alternatively from about 11 centipoise to about 5,000 centipoise,alternatively from about 12 centipoise to 2,500 centipoise,alternatively from about 13 centipoise to about 1,500 centipoise, andalternatively from about 14 centipoise to about 1,000 centipoise. Thehair composition viscosity values may be measured using a TA InstrumentsAR-G2 Rheometer with a concentric cylinder attachment at a shear rate of100 reciprocal seconds at 25° C.

1. Water Miscible Solvents

The compositions can include water miscible glycols and other diols.Non-limiting examples include dipropylene glycol, tripropylene glycol,diethylene glycol, ethylene glycol, propylene glycol, glycerin,1,3-propane diol, 2,2-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 2,3-butanediol, 2-methyl-2,4-pentanediol, and mixturesthereof. The hair care composition may comprise two or more watermiscible solvents, wherein at least one of the solvents is dipropyleneglycol.

2. Hydrotropes

The compositions can include hydrotropes. Non-limiting examples includelower aliphatic alcohols, lower alkylbenzene sulphonates (derivatives ofxylene and toluene) and combinations of these. Preferred are alcohol,urea, sodium xylene sulphonate, ammonium xylene sulfonate, and potassiumxylene sulfonate.

3. Class A Materials

The Class A viscosity reducing agents may have a partition dispersioncoefficient of from about −5 to about −0.7, alternatively from about−4.6 to about −0.85, alternatively from about −4.5 to about −0.9,alternatively from about −3.1 to about −0.7, and alternatively fromabout −3 to about −0.85. The Class A viscosity reducing agents may havea partition dispersion coefficient of from about −4.6 to about −1.9,alternatively from about −4.5 to about −2, wherein the one or moreviscosity reducing agents has at least 2 polar groups, or has 1 polargroup and less than 5 acyclic sp3 hybridized carbon atoms that areconnected to each other in a contiguous group. The Class A viscosityreducing agents may have a partition dispersion coefficient of fromabout −4.6 to about −1.9, alternatively from about −4.5 to about −2,wherein the one or more viscosity reducing agents has 2 to 4 polargroups, or has 1 polar group and 1 to 3 acyclic sp3 hybridized carbonatoms that are connected to each other in a contiguous group. The ClassA viscosity reducing agents may have a partition dispersion coefficientof from about −4.6 to about −1.9, alternatively from about −4.5 to about−2, wherein the one or more viscosity reducing agents has 2 to 4 polargroups, or has 1 polar group and 2 acyclic sp3 hybridized carbon atomsthat are connected to each other in a contiguous group. The Class Aviscosity reducing agents may provide unexpected viscosity reductionwhen used in the hair care composition described herein.

The partition dispersion coefficient (PDC) is defined by the followingequation:

PDC=log P−0.3001*(δD)2+10.362*δD−93.251

wherein log P is the octanol water partitioning coefficient as computedby the Consensus algorithm implemented in ACD/Percepta version 14.02 byAdvanced Chemistry Development, Inc. (ACD/Labs, Toronto, Canada), andwherein δD is the Hansen solubility dispersion parameter in (MPa)1/2computed using Steven Abbott and Hiroshi Yamamoto's “HSPIP—HansenSolubility Parameters in Practice” program, 4th Edition, version 4.1.07.

The viscosity reducing agents may be organic compounds comprising 1polar group, alternatively at least 1 polar group, alternatively 2 to 4polar groups, and alternative alternatively at least 2 polar groups. Thepolar groups may be selected from the group consisting of alcohols,aldehydes, esters, lactones, coumarins, ethers, ketones, phenol, phenyl,oxides, alkenyl, alkynyl, and combinations thereof. The viscosityreducing agents may have a molecular weight of between 100 daltons and300 daltons, alternatively from about 125 daltons to about 300 daltons.Additionally, the viscosity reducing agents may have a water solubilityat between 23 and 25 degrees Celsius of from about 900 to 50,000 mg/L.

The Class A viscosity reducing agents may be selected from the groupconsisting of raspberry ketone, triethyl citrate, 5-methyl-3-heptanoneoxime, hydroxycitronellal, camphor gum, 2-isopropyl-5-methyl-2-hexenal,eucalyptol, 1,1-dimethoxyoctane, isobutyl hexanoate, dihyro isojasmonate, and combinations thereof. Alternatively, the Class Aviscosity reducing agents may be selected from the group consisting ofraspberry ketone, triethyl citrate, hydroxycitronellal, ethanol,dipropylene glycol, and combinations thereof.

4. Class B Materials

The Class B viscosity reducing agents may have a partition dispersioncoefficient of from about 0.05 to about 5.1, alternatively from about0.08 to about 4.5, alternatively from about 0.09 to about 4.4,alternatively from about 0.05 to about 2.0, alternatively from about0.08 to about 1.8, alternatively from about 0.09 to about 1.7, andalternatively from about 0.095 to about 1.68. The Class B viscosityreducing agents may provide unexpected viscosity reduction when used inthe hair care composition described herein.

The partition dispersion coefficient (PDC) is defined by the followingequation:

PDC=log P−0.3001*(δD)²+10.362*δD−93.251

wherein log P is the octanol water partitioning coefficient as computedby the Consensus algorithm implemented in ACD/Percepta version 14.02 byAdvanced Chemistry Development, Inc. (ACD/Labs, Toronto, Canada), andwherein δD is the Hansen solubility dispersion parameter in (MPa)^(1/2)computed using Steven Abbott and Hiroshi Yamamoto's “HSPIP—HansenSolubility Parameters in Practice” program, 4^(th) Edition, version4.1.07.

The viscosity reducing agents may be organic compounds comprising 1polar group, alternatively at least 1 polar group, alternatively 2 to 4polar groups, and alternative alternatively at least 2 polar groups. Thepolar groups may be selected from the group consisting of alcohols,aldehydes, esters, lactones, coumarins, ethers, ketones, phenol, phenyl,oxides, alkenyl, alkynyl, and combinations thereof. The viscosityreducing agents may have a molecular weight of between 100 daltons and300 daltons, alternatively from about 125 daltons to about 300 daltons.Additionally, the viscosity reducing agents may have a water solubilityat between 23 and 25 degrees Celsius of from about 10 to 900 mg/L.

The Class B viscosity reducing agents may be selected from the groupconsisting of veloutone, isoamyl salicylate, gamma-terpinene, linalyliso butyrate, alpha-terpinene, limonene, dipentene, geranyl phenylacetate, iso propyl myristate, hexadecane, and combinations thereof.Alternatively, the Class B viscosity reducing agents may be selectedfrom the group consisting of veloutone, gamma-terpinene, linalyl isobutyrate, alpha-terpinene, limonene, dipentene, geranyl phenyl acetate,iso propyl myristate, hexadecane, and combinations thereof.Alternatively, the Class B viscosity reducing agents may be selectedfrom the group consisting of veloutone, isoamyl salicylate,gamma-terpinene, linalyl iso butyrate, alpha-terpinene, limonene,dipentene, geranyl phenyl acetate, and combinations thereof.

5. Silicone Polyethers

In a further embodiment of the present invention, the personal carecomposition may comprise silicone polyethers. Non-limiting examplesinclude PEG-8 Dimethicones with molecular weights between 500 g/mol and3500 g/mol including, Silsurf A208 (MW of about 855 g/mol) and SilsurfD208 (MW of about 2706 g/mol).

C. Water Carrier

The hair care compositions can include from about 45% to about 78%,alternatively from about 50% to about 75%, alternatively from about 55%to about 70%, alternatively from about 60% to about 68% water by weightof the hair care composition.

D. Cationic Polymers

The hair care composition can also comprise a cationic polymer. Thesecationic polymers can include at least one of (a) a cationic guarpolymer, (b) a cationic non-guar galactomannan polymer, (c) a cationictapioca polymer, (d) a cationic copolymer of acrylamide monomers andcationic monomers, and/or (e) a synthetic, non-crosslinked, cationicpolymer, which may or may not form lyotropic liquid crystals uponcombination with the detersive surfactant (f) a cationic cellulosepolymer. Additionally, the cationic polymer can be a mixture of cationicpolymers.

The hair care composition may comprise a cationic guar polymer, which isa cationically substituted galactomannan (guar) gum derivatives. Guargum for use in preparing these guar gum derivatives is typicallyobtained as a naturally occurring material from the seeds of the guarplant. The guar molecule itself is a straight chain mannan, which isbranched at regular intervals with single membered galactose units onalternative mannose units. The mannose units are linked to each other bymeans of β(1-4) glycosidic linkages. The galactose branching arises byway of an α(1-6) linkage. Cationic derivatives of the guar gums areobtained by reaction between the hydroxyl groups of thepolygalactomannan and reactive quaternary ammonium compounds. The degreeof substitution of the cationic groups onto the guar structure should besufficient to provide the requisite cationic charge density describedabove.

According to one embodiment, the cationic polymer, including but notlimited to a cationic guar polymer, has a molecular weight of less than1.0 million g/mol, or from about 10 thousand to about 1 million g/mol,or from about 25 thousand to about 1 million g/mol, or from about 50thousand to about 1 million g/mol, or from about 100 thousand to about 1million g/mol. In one embodiment, the cationic guar polymer has a chargedensity of from about 0.2 to about 2.2 meq/g, or from about 0.3 to about2.0 meq/g, or from about 0.4 to about 1.8 meq/g; or from about 0.5 meq/gto about 1.7 meq/g.

According to one embodiment, the cationic guar polymer has a weightaverage molecular weight of less than about 1.0 million g/mol, and has acharge density of from about 0.1 meq/g to about 2.5 meq/g. In anembodiment, the cationic guar polymer has a weight average molecularweight of less than 950 thousand g/mol, or from about 10 thousand toabout 900 thousand g/mol, or from about 25 thousand to about 900thousand g/mol, or from about 50 thousand to about 900 thousand g/mol,or from about 100 thousand to about 900 thousand g/mol. from about 150thousand to about 800 thousand g/mol. In one embodiment, the cationicguar polymer has a charge density of from about 0.2 to about 2.2 meq/g,or from about 0.3 to about 2.0 meq/g, or from about 0.4 to about 1.8meq/g; or from about 0.5 meq/g to about 1.5 meq/g.

The hair care composition can comprise from about 0.01% to about 1%,alternatively from about 0.05% to about 1%, alternatively from about0.05% to about 0.9%, alternatively from about 0.1% to about 0.8%, oralternatively from about 0.2% to about 0.7% of cationic polymer (a), bytotal weight of the hair care composition.

The cationic guar polymer may be formed from quaternary ammoniumcompounds. In an embodiment, the quaternary ammonium compounds forforming the cationic guar polymer conform to the general formula 1:

wherein where R³, R⁴ and R⁵ are methyl or ethyl groups; R⁶ is either anepoxyalkyl group of the general formula 2:

or R⁶ is a halohydrin group of the general formula 3:

wherein R⁷ is a C₁ to C₃ alkylene; X is chlorine or bromine, and Z is ananion such as Cl—, Br—, I— or HSO₄—.

In an embodiment, the cationic guar polymer conforms to the generalformula 4:

wherein R⁸ is guar gum; and wherein R⁴, R⁵, R⁶ and R⁷ are as definedabove; and wherein Z is a halogen. In an embodiment, the cationic guarpolymer conforms to Formula 5:

Suitable cationic guar polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride. In an embodiment, thecationic guar polymer is a guar hydroxypropyltrimonium chloride.Specific examples of guar hydroxypropyltrimonium chlorides include theJaguar® series commercially available from Rhone-Poulenc Incorporated,for example Jaguar® C-500, commercially available from Rhodia. Jaguar®C-500 has a charge density of 0.8 meq/g and a molecular weight of500,000 g/mol. Other suitable guar hydroxypropyltrimonium chloride are:guar hydroxypropyltrimonium chloride which has a charge density of about1.1 meq/g and a molecular weight of about 500,000 g/mol is availablefrom ASI, a charge density of about 1.5 meq/g and a molecular weight ofabout 500,000 g/mole is available from ASI. Other suitable guarhydroxypropyltrimonium chloride are: Hi-Care 1000, which has a chargedensity of about 0.7 meq/g and a Molecular weight of about 600,000g/mole and is available from Rhodia; N-Hance 3269 and N-Hance 3270,which has a charge density of about 0.7 meq/g and a molecular weight ofabout 425,000 g/mol and is available from ASIAquaCat CG518 has a chargedensity of about 0.9 meq/g and a Molecular weight of about 50,000 g/moland is available from ASI. BF-13, which is a borate (boron) free guar ofcharge density of about 1.1 meq/g and molecular weight of about 800,000and BF-17, which is a borate (boron) free guar of charge density ofabout 1.7 meq/g and M. W.t of about 800,000 both available from ASI.

The hair care compositions may comprise a galactomannan polymerderivative having a mannose to galactose ratio of greater than 2:1 on amonomer to monomer basis, the galactomannan polymer derivative selectedfrom the group consisting of a cationic galactomannan polymer derivativeand an amphoteric galactomannan polymer derivative having a net positivecharge. As used herein, the term “cationic galactomannan” refers to agalactomannan polymer to which a cationic group is added. The term“amphoteric galactomannan” refers to a galactomannan polymer to which acationic group and an anionic group are added such that the polymer hasa net positive charge.

Galactomannan polymers are present in the endosperm of seeds of theLeguminosae family Galactomannan polymers are made up of a combinationof mannose monomers and galactose monomers. The galactomannan moleculeis a straight chain mannan branched at regular intervals with singlemembered galactose units on specific mannose units. The mannose unitsare linked to each other by means of β (1-4) glycosidic linkages. Thegalactose branching arises by way of an α (1-6) linkage. The ratio ofmannose monomers to galactose monomers varies according to the speciesof the plant and also is affected by climate. Non Guar Galactomannanpolymer derivatives suitable for use can have a ratio of mannose togalactose of greater than 2:1 on a monomer to monomer basis. Suitableratios of mannose to galactose can be greater than about 3:1, and theratio of mannose to galactose can be greater than about 4:1. Analysis ofmannose to galactose ratios is well known in the art and is typicallybased on the measurement of the galactose content.

The gum for use in preparing the non-guar galactomannan polymerderivatives is typically obtained as naturally occurring material suchas seeds or beans from plants. Examples of various non-guargalactomannan polymers include but are not limited to Tara gum (3 partsmannose/1 part galactose), Locust bean or Carob (4 parts mannose/1 partgalactose), and Cassia gum (5 parts mannose/1 part galactose).

In one embodiment of the invention, the non-guar galactomannan polymerderivatives have a M. Wt. from about 1,000 to about 1,000,000, and/orform about 5,000 to about 900,000.

The hair care compositions of the can also include galactomannan polymerderivatives which have a cationic charge density from about 0.5 meq/g toabout 7 meq/g., The galactomannan polymer derivatives can have acationic charge density from about 1 meq/g to about 5 meq/g. The degreeof substitution of the cationic groups onto the galactomannan structureshould be sufficient to provide the requisite cationic charge density.

The galactomannan polymer derivative can be a cationic derivative of thenon-guar galactomannan polymer, which is obtained by reaction betweenthe hydroxyl groups of the polygalactomannan polymer and reactivequaternary ammonium compounds. Suitable quaternary ammonium compoundsfor use in forming the cationic galactomannan polymer derivativesinclude those conforming to the general formulas 1-5, as defined above.

Cationic non-guar galactomannan polymer derivatives formed from thereagents described above are represented by the general formula 6:

wherein R is the gum. The cationic galactomannan derivative can be a gumhydroxypropyltrimethylammonium chloride, which can be more specificallyrepresented by the general formula 7:

Alternatively the galactomannan polymer derivative can be an amphotericgalactomannan polymer derivative having a net positive charge, obtainedwhen the cationic galactomannan polymer derivative further comprises ananionic group.

The cationic non-guar galactomannan can have a ratio of mannose togalactose is greater than about 4:1, a molecular weight of about 50,000g/mol to about 1,000,000 g/mol, and/or from about 100,000 g/mol to about900,000 g/mol and a cationic charge density from about 1 meq/g to about5 meq/g, and/or from 2 meq/g to about 4 meq/g and can also be derivedfrom a cassia plant.

The hair care compositions can comprise at least about 0.05% of agalactomannan polymer derivative by weight of the composition,alternatively from about 0.05% to about 2%, by weight of thecomposition, of a galactomannan polymer derivative.

The hair care compositions can comprise water-soluble cationicallymodified starch polymers. As used herein, the term “cationicallymodified starch” refers to a starch to which a cationic group is addedprior to degradation of the starch to a smaller molecular weight, orwherein a cationic group is added after modification of the starch toachieve a desired molecular weight. The definition of the term“cationically modified starch” also includes amphoterically modifiedstarch. The term “amphoterically modified starch” refers to a starchhydrolysate to which a cationic group and an anionic group are added.

The hair care compositions can comprise cationically modified starchpolymers at a range of about 0.01% to about 10%, and/or from about 0.05%to about 5%, by weight of the composition.

The cationically modified starch polymers disclosed herein have apercent of bound nitrogen of from about 0.5% to about 4%.

The cationically modified starch polymers for use in the hair carecompositions can have a molecular weight about 50,000 g/mol to about1,000,000 g/mol and/or from about 100,000 g/mol to about 1,000,000g/mol.

The hair care compositions can include cationically modified starchpolymers which have a charge density of from about 0.2 meq/g to about 5meq/g, and/or from about 0.2 meq/g to about 2 meq/g. The chemicalmodification to obtain such a charge density includes, but is notlimited to, the addition of amino and/or ammonium groups into the starchmolecules. Non-limiting examples of these ammonium groups may includesubstituents such as hydroxypropyl trimmonium chloride,trimethylhydroxypropyl ammonium chloride, dimethylstearylhydroxypropylammonium chloride, and dimethyldodecylhydroxypropyl ammonium chloride.See Solarek, D. B., Cationic Starches in Modified Starches: Propertiesand Uses, Wurzburg, O. B., Ed., CRC Press, Inc., Boca Raton, Fla. 1986,pp 113-125. The cationic groups may be added to the starch prior todegradation to a smaller molecular weight or the cationic groups may beadded after such modification.

The cationically modified starch polymers generally have a degree ofsubstitution of a cationic group from about 0.2 to about 2.5. As usedherein, the “degree of substitution” of the cationically modified starchpolymers is an average measure of the number of hydroxyl groups on eachanhydroglucose unit which is derivatized by substituent groups. Sinceeach anhydroglucose unit has three potential hydroxyl groups availablefor substitution, the maximum possible degree of substitution is 3. Thedegree of substitution is expressed as the number of moles ofsubstituent groups per mole of anhydroglucose unit, on a molar averagebasis. The degree of substitution may be determined using proton nuclearmagnetic resonance spectroscopy (“.sup.1H NMR”) methods well known inthe art. Suitable .sup.1H NMR techniques include those described in“Observation on NMR Spectra of Starches in Dimethyl Sulfoxide,Iodine-Complexing, and Solvating in Water-Dimethyl Sulfoxide”, Qin-JiPeng and Arthur S. Perlin, Carbohydrate Research, 160 (1987), 57-72; and“An Approach to the Structural Analysis of Oligosaccharides by NMRSpectroscopy”, J. Howard Bradbury and J. Grant Collins, CarbohydrateResearch, 71, (1979), 15-25.

The source of starch before chemical modification can be chosen from avariety of sources such as tubers, legumes, cereal, and grains.Non-limiting examples of this source starch may include corn starch,wheat starch, rice starch, waxy corn starch, oat starch, cassaya starch,waxy barley, waxy rice starch, glutenous rice starch, sweet rice starch,amioca, potato starch, tapioca starch, oat starch, sago starch, sweetrice, or mixtures thereof.

The cationically modified starch polymers can be selected from degradedcationic maize starch, cationic tapioca, cationic potato starch, andmixtures thereof. Alternatively, the cationically modified starchpolymers are cationic corn starch and cationic tapioca.

The starch, prior to degradation or after modification to a smallermolecular weight, may comprise one or more additional modifications. Forexample, these modifications may include cross-linking, stabilizationreactions, phosphorylations, and hydrolyzations. Stabilization reactionsmay include alkylation and esterification.

The cationically modified starch polymers may be incorporated into thecomposition in the form of hydrolyzed starch (e.g., acid, enzyme, oralkaline degradation), oxidized starch (e.g., peroxide, peracid,hypochlorite, alkaline, or any other oxidizing agent),physically/mechanically degraded starch (e.g., via the thermo-mechanicalenergy input of the processing equipment), or combinations thereof.

An optimal form of the starch is one which is readily soluble in waterand forms a substantially clear (% Transmittance.gtoreq.80 at 600 nm)solution in water. The transparency of the composition is measured byUltra-Violet/Visible (UV/VIS) spectrophotometry, which determines theabsorption or transmission of UV/VIS light by a sample, using a GretagMacbeth Colorimeter Color i 5 according to the related instructions. Alight wavelength of 600 nm has been shown to be adequate forcharacterizing the degree of clarity of cosmetic compositions.

Suitable cationically modified starch for use in hair care compositionsare available from known starch suppliers. Also suitable for use in haircare compositions are nonionic modified starch that can be furtherderivatized to a cationically modified starch as is known in the art.Other suitable modified starch starting materials may be quaternized, asis known in the art, to produce the cationically modified starch polymersuitable for use in hair care compositions.

Starch Degradation Procedure: a starch slurry can be prepared by mixinggranular starch in water. The temperature is raised to about 35° C. Anaqueous solution of potassium permanganate is then added at aconcentration of about 50 ppm based on starch. The pH is raised to about11.5 with sodium hydroxide and the slurry is stirred sufficiently toprevent settling of the starch. Then, about a 30% solution of hydrogenperoxide diluted in water is added to a level of about 1% of peroxidebased on starch. The pH of about 11.5 is then restored by addingadditional sodium hydroxide. The reaction is completed over about a 1 toabout 20 hour period. The mixture is then neutralized with dilutehydrochloric acid. The degraded starch is recovered by filtrationfollowed by washing and drying.

The hair care composition can comprise a cationic copolymer of anacrylamide monomer and a cationic monomer, wherein the copolymer has acharge density of from about 1.0 meq/g to about 3.0 meq/g. The cationiccopolymer can be a synthetic cationic copolymer of acrylamide monomersand cationic monomers.

The cationic copolymer can comprise:

-   -   (i) an acrylamide monomer of the following Formula AM:

-   -   where R⁹ is H or C₁₋₄ alkyl; and R¹⁰ and R¹¹ are independently        selected from the group consisting of H, C₁₋₄ alkyl, CH₂OCH₃,        CH₂OCH₂CH(CH₃)₂, and phenyl, or together are C₃₋₆ cycloalkyl;        and    -   (ii) a cationic monomer conforming to Formula CM:

where k=1, each of v, v′, and v″ is independently an integer of from 1to 6, w is zero or an integer of from 1 to 10, and X⁻ is an anion.

The cationic monomer can conform to Formula CM and where k=1, v=3 andw=0, z=1 and X⁻ is Cl⁻ to form the following structure:

The above structure may be referred to as diquat. Alternatively, thecationic monomer can conform to Formula CM and wherein v and v″ are each3, v′=1, w=1, y=1 and X⁻ is Cl⁻, such as:

The above structure may be referred to as triquat.

Suitable acrylamide monomer include, but are not limited to, eitheracrylamide or methacrylamide.

In an alternative embodiment, the cationic copolymer is of an acrylamidemonomer and a cationic monomer, wherein the cationic monomer is selectedfrom the group consisting of: dimethylaminoethyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, ditertiobutylaminoethyl(meth)acrylate, dimethylaminomethyl (meth)acrylamide,dimethylaminopropyl (meth)acrylamide; ethylenimine, vinylamine,2-vinylpyridine, 4-vinylpyridine; trimethylammonium ethyl (meth)acrylatechloride, trimethylammonium ethyl (meth)acrylate methyl sulphate,dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethyl ammonium ethyl(meth)acrylamido chloride, trimethyl ammonium propyl (meth)acrylamidochloride, vinylbenzyl trimethyl ammonium chloride, diallyldimethylammonium chloride, and mixtures thereof.

The cationic copolymer can comprise a cationic monomer selected from thegroup consisting of: cationic monomers include trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride, andmixtures thereof.

The cationic copolymer can be water-soluble. The cationic copolymer isformed from (1) copolymers of (meth)acrylamide and cationic monomersbased on (meth)acrylamide, and/or hydrolysis-stable cationic monomers,(2) terpolymers of (meth)acrylamide, monomers based on cationic(meth)acrylic acid esters, and monomers based on (meth)acrylamide,and/or hydrolysis-stable cationic monomers. Monomers based on cationic(meth)acrylic acid esters may be cationized esters of the (meth)acrylicacid containing a quaternized N atom. In an embodiment, cationizedesters of the (meth)acrylic acid containing a quaternized N atom arequaternized dialkylaminoalkyl (meth)acrylates with C1 to C3 in the alkyland alkylene groups. Suitable cationized esters of the (meth)acrylicacid containing a quaternized N atom can be selected from the groupconsisting of: ammonium salts of dimethylaminomethyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate,diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; anddiethylaminopropyl (meth)acrylate quaternized with methyl chloride. Inan embodiment, the cationized esters of the (meth)acrylic acidcontaining a quaternized N atom is dimethylaminoethyl acrylate, which isquaternized with an alkyl halide, or with methyl chloride or benzylchloride or dimethyl sulfate (ADAME-Quat). the cationic monomer whenbased on (meth)acrylamides can be quaternizeddialkylaminoalkyl(meth)acrylamides with C1 to C3 in the alkyl andalkylene groups, or dimethylaminopropylacrylamide, which is quaternizedwith an alkyl halide, or methyl chloride or benzyl chloride or dimethylsulfate.

Suitable cationic monomer based on a (meth)acrylamide includequaternized dialkylaminoalkyl(meth)acrylamide with C1 to C3 in the alkyland alkylene groups. The cationic monomer based on a (meth)acrylamidecan be dimethylaminopropylacrylamide, which is quaternized with an alkylhalide, especially methyl chloride or benzyl chloride or dimethylsulfate.

The cationic monomer can be a hydrolysis-stable cationic monomer.Hydrolysis-stable cationic monomers can be, in addition to adialkylaminoalkyl(meth)acrylamide, all monomers that can be regarded asstable to the OECD hydrolysis test. The cationic monomer can behydrolysis-stable and the hydrolysis-stable cationic monomer can beselected from the group consisting of: diallyldimethylammonium chlorideand water-soluble, cationic styrene derivatives.

The cationic copolymer can be a terpolymer of acrylamide,2-dimethylammoniumethyl (meth)acrylate quaternized with methyl chloride(ADAME-Q) and 3-dimethylammoniumpropyl(meth)acrylamide quaternized withmethyl chloride (DIMAPA-Q). The cationic copolymer can be formed fromacrylamide and acrylamidopropyltrimethylammonium chloride, wherein theacrylamidopropyltrimethylammonium chloride has a charge density of fromabout 1.0 meq/g to about 3.0 meq/g.

The cationic copolymer can have a charge density of from about 1.1 meq/gto about 2.5 meq/g, or from about 1.1 meq/g to about 2.3 meq/g, or fromabout 1.2 meq/g to about 2.2 meq/g, or from about 1.2 meq/g to about 2.1meq/g, or from about 1.3 meq/g to about 2.0 meq/g, or from about 1.3meq/g to about 1.9 meq/g.

The cationic copolymer can have a molecular weight from about 10thousand g/mol to about 1 million g/mol, or from about 25 thousand g/molto about 1 million g/mol, or from about 50 thousand g/mol to about 1million g/mol, or from about 100 thousand g/mol to about 1.0 milliong/mol, or from about 150 thousand g/mol to about 1.0 million g/mol.

(a) Cationic Synthetic Polymers

The hair care composition can comprise a cationic synthetic polymer thatmay be formed from

i) one or more cationic monomer units, and optionally

ii) one or more monomer units bearing a negative charge, and/or

iii) a nonionic monomer,

wherein the subsequent charge of the copolymer is positive. The ratio ofthe three types of monomers is given by “m”, “p” and “q” where “m” isthe number of cationic monomers, “p” is the number of monomers bearing anegative charge and “q” is the number of nonionic monomers

The cationic polymers can be water soluble or dispersible,non-crosslinked, and synthetic cationic polymers having the followingstructure:

where A, may be one or more of the following cationic moieties:

where @=amido, alkylamido, ester, ether, alkyl or alkylaryl;where Y=C1-C22 alkyl, alkoxy, alkylidene, alkyl or aryloxy;where ψ=C1-C22 alkyl, alkyloxy, alkyl aryl or alkyl arylox;where Z=C1-C22 alkyl, alkyloxy, aryl or aryloxy;where R1=H, C1-C4 linear or branched alkyl;where s=0 or 1, n=0 or ≥1;where T and R7=C1-C22 alkyl; andwhere X—=halogen, hydroxide, alkoxide, sulfate or alkylsulfate.

Where the monomer bearing a negative charge is defined by R2′=H, C1-C4linear or branched alkyl and R₃ as:

where D=O, N, or S;where Q=NH₂ or O;where u=1-6;where t=0-1; andwhere J=oxygenated functional group containing the following elements P,S, C.

Where the nonionic monomer is defined by R2″=H, C1-C4 linear or branchedalkyl, R6=linear or branched alkyl, alkyl aryl, aryl oxy, alkyloxy,alkylaryl oxy and β is defined as

andwhere G′ and G″ are, independently of one another, O, S or N—H and L=0or 1.

Examples of cationic monomers include aminoalkyl (meth)acrylates,(meth)aminoalkyl (meth)acrylamides; monomers comprising at least onesecondary, tertiary or quaternary amine function, or a heterocyclicgroup containing a nitrogen atom, vinylamine or ethylenimine;diallyldialkyl ammonium salts; their mixtures, their salts, andmacromonomers deriving from therefrom.

Further examples of cationic monomers include dimethylaminoethyl(meth)acrylate, dimethylaminopropyl (meth)acrylate,ditertiobutylaminoethyl (meth)acrylate, dimethylaminomethyl(meth)acrylamide, dimethylaminopropyl (meth)acrylamide, ethylenimine,vinylamine, 2-vinylpyridine, 4-vinylpyridine, trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride,diallyldimethyl ammonium chloride.

Suitable cationic monomers include those which comprise a quaternaryammonium group of formula —NR₃ ⁺, wherein R, which is identical ordifferent, represents a hydrogen atom, an alkyl group comprising 1 to 10carbon atoms, or a benzyl group, optionally carrying a hydroxyl group,and comprise an anion (counter-ion). Examples of anions are halides suchas chlorides, bromides, sulphates, hydrosulphates, alkylsulphates (forexample comprising 1 to 6 carbon atoms), phosphates, citrates, formates,and acetates.

Suitable cationic monomers include trimethylammonium ethyl(meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methylsulphate, dimethylammonium ethyl (meth)acrylate benzyl chloride,4-benzoylbenzyl dimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamido chloride, trimethyl ammonium propyl(meth)acrylamido chloride, vinylbenzyl trimethyl ammonium chloride.

Additional suitable cationic monomers include trimethyl ammonium propyl(meth)acrylamido chloride.

Examples of monomers bearing a negative charge include alphaethylenically unsaturated monomers comprising a phosphate or phosphonategroup, alpha ethylenically unsaturated monocarboxylic acids,monoalkylesters of alpha ethylenically unsaturated dicarboxylic acids,monoalkylamides of alpha ethylenically unsaturated dicarboxylic acids,alpha ethylenically unsaturated compounds comprising a sulphonic acidgroup, and salts of alpha ethylenically unsaturated compounds comprisinga sulphonic acid group.

Suitable monomers with a negative charge include acrylic acid,methacrylic acid, vinyl sulphonic acid, salts of vinyl sulfonic acid,vinylbenzene sulphonic acid, salts of vinylbenzene sulphonic acid,alpha-acrylamidomethylpropanesulphonic acid, salts ofalpha-acrylamidomethylpropanesulphonic acid, 2-sulphoethyl methacrylate,salts of 2-sulphoethyl methacrylate, acrylamido-2-methylpropanesulphonicacid (AMPS), salts of acrylamido-2-methylpropanesulphonic acid, andstyrenesulphonate (SS).

Examples of nonionic monomers include vinyl acetate, amides of alphaethylenically unsaturated carboxylic acids, esters of an alphaethylenically unsaturated monocarboxylic acids with an hydrogenated orfluorinated alcohol, polyethylene oxide (meth)acrylate (i.e.polyethoxylated (meth)acrylic acid), monoalkylesters of alphaethylenically unsaturated dicarboxylic acids, monoalkylamides of alphaethylenically unsaturated dicarboxylic acids, vinyl nitriles, vinylamineamides, vinyl alcohol, vinyl pyrolidone, and vinyl aromatic compounds.

Suitable nonionic monomers include styrene, acrylamide, methacrylamide,acrylonitrile, methylacrylate, ethylacrylate, n-propylacrylate,n-butylacrylate, methylmethacrylate, ethylmethacrylate,n-propylmethacrylate, n-butylmethacrylate, 2-ethyl-hexyl acrylate,2-ethyl-hexyl methacrylate, 2-hydroxyethylacrylate and2-hydroxyethylmethacrylate.

The anionic counterion (X—) in association with the synthetic cationicpolymers may be any known counterion so long as the polymers remainsoluble or dispersible in water, in the hair care composition, or in acoacervate phase of the hair care composition, and so long as thecounterions are physically and chemically compatible with the essentialcomponents of the hair care composition or do not otherwise undulyimpair product performance, stability or aesthetics. Non limitingexamples of such counterions include halides (e.g., chlorine, fluorine,bromine, iodine), sulfate and methylsulfate.

The concentration of the cationic polymers ranges about 0.025% to about5%, from about 0.1% to about 3%, and/or from about 0.2% to about 1%, byweight of the hair care composition.

Suitable cationic cellulose polymers are salts of hydroxyethyl cellulosereacted with trimethyl ammonium substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 10 and available from Dow/AmercholCorp. (Edison, N.J., USA) in their Polymer LR, JR, and KG series ofpolymers. Other suitable types of cationic cellulose include thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromDow/Amerchol Corp. under the tradename Polymer LM-200. Other suitabletypes of cationic cellulose include the polymeric quaternary ammoniumsalts of hydroxyethyl cellulose reacted with lauryl dimethylammonium-substituted epoxide and trimethyl ammonium substituted epoxidereferred to in the industry (CTFA) as Polyquaternium 67. These materialsare available from Dow/Amerchol Corp. under the tradename SoftCATPolymer SL-5, SoftCAT Polymer SL-30, Polymer SL-60, Polymer SL-100,Polymer SK-L, Polymer SK-M, Polymer SK-MH, and Polymer SK-H.

E. Conditioning Agents

The hair care compositions may comprise one or more conditioning agent.Conditioning agents include materials that are used to give a particularconditioning benefit to hair and/or skin. The conditioning agents usefulin the hair care compositions of the present invention typicallycomprise a water-insoluble, water-dispersible, non-volatile, liquid thatforms emulsified, liquid particles. Suitable conditioning agents for usein the hair care composition are those conditioning agents characterizedgenerally as silicones (e.g., silicone oils, cationic silicones,silicone gums, high refractive silicones, and silicone resins), organicconditioning oils (e.g., hydrocarbon oils, polyolefins, and fattyesters) or combinations thereof, or those conditioning agents whichotherwise form liquid, dispersed particles in the aqueous surfactantmatrix.

1. Silicone Conditioning Agents

The hair care composition can comprise from about 0% to about 20% byweight, alternatively from about 6% to about 18% by weight; andalternatively from about 8% to about 16% by weight of one of moresilicones with a particle size of less than about 300 nm, alternativelyless than about 200 nm, and alternatively less than about 100 nm. Thesilicone can be in the form of a nanoemulsion.

The particle size of the one or more silicones may be measured bydynamic light scattering (DLS). A Malvern Zetasizer Nano ZEN3600 system(www.malvern.com) using He—Ne laser 633 nm may be used for themeasurement at 25° C.

The autocorrelation function may be analyzed using the ZetasizerSoftware provided by Malvern Instruments, which determines the effectivehydrodynamic radius, using the Stokes-Einstein equation:

$D - \frac{k_{B}T}{6{\pi\eta}\; R}$

wherein k_(B) is the Boltzmann Constant, T is the absolute temperature,η is the viscosity of the medium, D is the mean diffusion coefficient ofthe scattering species, and R is the hydrodynamic radius of particles.

Particle size (i.e. hydrodynamic radius) may be obtained by correlatingthe observed speckle pattern that arises due to Brownian motion andsolving the Stokes-Einstein equation, which relates the particle size tothe measured diffusion constant, as is known in the art.

For each sample, 3 measurements may be made and Z-average values may bereported as the particle size.

In an embodiment, the one or more silicones may be in the form of ananoemulsion. The nanoemulsion may comprise any silicone suitable forapplication to the skin and/or hair.

In an embodiment, the one or more silicones may include in theirmolecular structure polar functional groups such as Si—OH (present indimethiconols), primary amines, secondary amines, tertiary amines, andquaternary ammonium salts. The one or more silicones may be selectedfrom the group consisting of aminosilicones, pendant quaternary ammoniumsilicones, terminal quaternary ammonium silicones, amino polyalkyleneoxide silicones, quaternary ammonium polyalkylene oxide silicones, andamino morpholino silicones.

The one or more silicones may comprise:

(a) at least one aminosilicone corresponding to formula (V):

R′_(a)G_(3-a)-Si(OSiG₂)_(n)-(OSiG_(b)R′_(2-b))_(m)—O—SiG_(3-a)R′_(a)  (I)

in which:

G is chosen from a hydrogen atom, a phenyl group, OH group, and C₁-C₈alkyl groups, for example methyl,a is an integer ranging from 0 to 3, and in one embodiment a is 0,b is chosen from 0 and 1, and in one embodiment b is 1,m and n are numbers such that the sum (n+m) can range for example from 1to 2 000, such as for example from 50 to 150, wherein n can be forexample chosen from numbers ranging from 0 to 1 999, such as for examplefrom 49 to 149, and wherein m can be chosen from numbers ranging forexample from 1 to 2 000, such as for example from 1 to 10;R′ is a monovalent group of formula —C_(q)H_(2q)L in which q is a numberfrom 2 to 8 and L is an optionally quaternized amine group chosen fromthe groups:—NR″—CH₂—CH₂—N′(R¹)₂,

—N(R″)₂,

—N⁺(R″)₃A⁻,—N⁺H(R″)₂A⁻,—N⁺H₂(R″)A⁻, and—N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,in which R″ can be chosen from a hydrogen atom, phenyl groups, benzylgroups, and saturated monovalent hydrocarbon-based groups, such as forexample an alkyl group comprising from 1 to 20 carbon atoms, and A⁻ ischosen from halide ions such as, for example, fluoride, chloride,bromide and iodide.

In an embodiment, the one or more silicones may include thosecorresponding to formula (1) wherein a=0, G=methyl, m and n are numberssuch that the sum (n+m) can range for example from 1 to 2 000, such asfor example from 50 to 150, wherein n can be for example chosen fromnumbers ranging from 0 to 1 999, such as for example from 49 to 149, andwherein m can be chosen from numbers ranging for example from 1 to 2000, such as for example from 1 to 10; and L is —N(CH₃)₂ or —NH₂,alternatively —NH₂.

Additional said at least one aminosilicone of the invention include:(b) pendant quaternary ammonium silicones of formula (VII):

in which:R₅ is chosen from monovalent hydrocarbon-based groups comprising from 1to 18 carbon atoms, such as C₁-C₁₈ alkyl groups and C₂-C₁₈ alkenylgroups, for example methyl;R₆ is chosen from divalent hydrocarbon-based groups, such as divalentC₁-C₁₈ alkylene groups and divalent C₁-C₁₈ alkylenoxy groups, forexample C₁-C₈ alkylenoxy groups, wherein said R₆ is bonded to the Si byway of an SiC bond;Q⁻ is an anion that can be for example chosen from halide ions, such aschloride, and organic acid salts (such as acetate);r is an average statistical value ranging from 2 to 20, such as from 2to 8;s is an average statistical value ranging from 20 to 200, such as from20 to 50.

Such aminosilicones are described more particularly in U.S. Pat. No.4,185,087, the disclosure of which is incorporated by reference herein.

A silicone which falls within this class is the silicone sold by thecompany Union Carbide under the name “Ucar Silicone ALE 56”.

Further examples of said at least one aminosilicone include:

c) quaternary ammonium silicones of formula (VIIb):

in which:groups R₇, which may be identical or different, are each chosen frommonovalent hydrocarbon-based groups comprising from 1 to 18 carbonatoms, such as C₁-C₁₈ alkyl groups, for example methyl, C₂-C₁₈ alkenylgroups, and rings comprising 5 or 6 carbon atoms;R₆ is chosen from divalent hydrocarbon-based groups, such as divalentC₁-C₁₈ alkylene groups and divalent C₁-C₁₈alkylenoxy, for example C₁-C₈,group connected to the Si by an SiC bond;R₈, which may be identical or different, represent a hydrogen atom, amonovalent hydrocarbon-based group comprising from 1 to 18 carbon atoms,and in particular a C₁-C₁₈ alkyl group, a C₂-C₁₈ alkenyl group or agroup —R₆—NHCOR₇;X⁻ is an anion such as a halide ion, in particular chloride, or anorganic acid salt (acetate, etc.);r represents an average statistical value from 2 to 200 and inparticular from 5 to 100.Such silicones are described, for example, in application EP-A-0 530974, the disclosure of which is incorporated by reference herein.Silicones falling within this class are the silicones sold by thecompany Eovnik under the names Abil Quat 3270, Abil Quat 3272, Abil Quat3474 and Abil ME 45.Further examples of said at least one aminosilicone include:d) quaternary ammonium and polyalkylene oxide siliconeswherein the quaternary nitrogen groups are located in the polysiloxanebackbone, at the termini, or both.Such silicones are described in PCT Publication No. WO 2002/010257, thedisclosure of which is incorporated by reference herein.Silicones falling within this class are the silicones sold by thecompany Momentive under the names Silsoft Q.(e) Aminofunctional silicones having morpholino groups of formula (V):

in which

A denotes a structural unit (I), (II), or (III) bound via —O—

-   -   or an oligomeric or polymeric residue, bound via —O—, containing        structural units of formulas (I), (II), or (III), or half of a        connecting oxygen atom to a structural unit (III), or denotes        —OH,    -   * denotes a bond to one of the structural units (I), (II), or        (III), or denotes a terminal group B (Si-bound) or D (O-bound),    -   B denotes an —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃        group,    -   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,    -   a, b, and c denote integers between 0 and 1000, with the        provision that a+b+c>0,    -   m, n, and o denote integers between 1 and 1000.

Aminofunctional silicones of this kind bear the INCI name:Amodimethicone/Morpholinomethyl Silsesquioxane Copolymer. A particularlysuitable amodimethicone is the product having the commercial name WackerBelsil® ADM 8301E.

Examples of such silicones are available from the following suppliers:

offered by the company Dow Corning: Fluids: 2-8566, AP 6087, AP 6088, DC8040 Fluid, fluid 8822A DC, DC 8803 & 8813 polymer, 7-6030, AP-8104, AP8201; Emulsions: CE-8170 AF Micro Emulsion, 2-8177, 2-8194Microemulsion, 9224 Emulsion, 939, 949, 959, DC 5-7113 QuatMicroemulsion, DC 5-7070 Emulsion, DC CE-8810, CE 8401 Emulsion, CE1619, Dow Corning Toray SS-3551, Dow Corning Toray SS-3552;offered by the company Wacker: Wacker Belsil ADM 652, ADM 656, 1100,1600, 1650 (fluids) ADM 6060 (linear amodimethicone) emulsion; ADM 6057E (branched amodimethicone) emulsion; ADM 8020 VP (micro emulsion); SLM28040 (micro emulsion);offered by the Company Momentive: Silsoft 331, SF1708, SME 253 & 254(emulsion), SM2125 (emulsion), SM 2658 (emulsion), Silsoft Q (emulsion)offered by the company Shin-Etsu: KF-889, KF-8675, KF-8004, X-52-2265(emulsion);offered by the Company Siltech Silicones: Siltech E-2145, E-Siltech2145-35;offered by the company Evonik Industries: Abil T Quat 60th

Some non-limiting examples of aminosilicones include the compoundshaving the following INCI names: Silicone Quaternium-1, SiliconeQuaternium-2, Silicone Quaternium-3, Silicone Quaternium-4, SiliconeQuaternium-5, Silicone Quaternium-6, Silicone Quaternium-7, SiliconeQuaternium-8, Silicone Quaternium-9, Silicone Quaternium-10, SiliconeQuaternium-11, Silicone Quaternium-12, Silicone Quaternium-15, SiliconeQuaternium-16, Silicone Quaternium-17, Silicone Quaternium-18, SiliconeQuaternium-20, Silicone Quaternium-21, Silicone Quaternium-22,Quaternium-80, as well as Silicone Quaternium-2 Panthenol Succinate andSilicone Quaternium-16/Glycidyl Dimethicone Crosspolymer.

The aminosilicones can be supplied in the form of a nanoemulsion andinclude MEM 9049, MEM 8177, MEM 0959, MEM 8194, SME 253, and Silsoft Q.

The one or more silicones may include dimethicones, and/ordimethiconols. The dimethiconols are hydroxyl terminateddimethylsilicones represented by the general chemical formulas

wherein R is an alkyl group (preferably R is methyl or ethyl, morepreferably methyl) and x is an integer up to about 500, chosen toachieve the desired molecular weight. Commercial dimethiconols typicallyare sold as mixtures with dimethicone or cyclomethicone (e.g., DowCorning® 1401, 1402, and 1403 fluids).

2. Non-Silicone Conditioning Agents

The conditioning agent of the hair care compositions described hereinmay also comprise at least one organic conditioning agents, either aloneor in combination with other conditioning agents, such as the siliconesdescribed above. Non-limiting examples of organic conditioning agentsare described below.a. Hydrocarbon Oils

Suitable organic conditioning agents for use as conditioning agents inhair care compositions include, but are not limited to, hydrocarbon oilshaving at least about 10 carbon atoms, such as cyclic hydrocarbons,straight chain aliphatic hydrocarbons (saturated or unsaturated), andbranched chain aliphatic hydrocarbons (saturated or unsaturated),including polymers and mixtures thereof. Straight chain hydrocarbon oilscan be from about C₁₂ to about C₁₉. Branched chain hydrocarbon oils,including hydrocarbon polymers, typically will contain more than 19carbon atoms.

b. PolyolefinsOrganic conditioning oils for use in the hair care compositionsdescribed herein also include liquid polyolefins, including liquidpoly-α-olefins and/or hydrogenated liquid poly-α-olefins. Polyolefinsfor use herein are prepared by polymerization of C₄ to about C₁₄olefenic monomers, and in one embodiment from about C₆ to about C₁₂.c. Fatty EstersOther suitable organic conditioning agents for use as a conditioningagent in the hair care compositions described herein include fattyesters having at least 10 carbon atoms. These fatty esters includeesters with hydrocarbyl chains derived from fatty acids or alcohols. Thehydrocarbyl radicals of the fatty esters hereof may include or havecovalently bonded thereto other compatible functionalities, such asamides and alkoxy moieties (e.g., ethoxy or ether linkages, etc.). Otheroligomeric or polymeric esters, prepared from unsaturated glycerylesters can also be used as conditioning materials.d. Fluorinated Conditioning Compounds

Fluorinated compounds suitable for delivering conditioning to hair asorganic conditioning agents include perfluoropolyethers, perfluorinatedolefins, fluorine based specialty polymers that may be in a fluid orelastomer form similar to the silicone fluids previously described, andperfluorinated dimethicones.

e. Fatty AlcoholsOther suitable organic conditioning oils for use in the hair carecompositions described herein include, but are not limited to, fattyalcohols having at least about 10 carbon atoms, about 10 to about 22carbon atoms, and in one embodiment about 12 to about 16 carbon atoms.f. Alkyl Glucosides and Alkyl Glucoside DerivativesSuitable organic conditioning oils for use in the hair care compositionsdescribed herein include, but are not limited to, alkyl glucosides andalkyl glucoside derivatives. Specific non-limiting examples of suitablealkyl glucosides and alkyl glucoside derivatives include Glucam E-10,Glucam E-20, Glucam P-10, and Glucquat 125 commercially available fromAmerchol.g. Polyethylene Glycols

Additional compounds useful herein as conditioning agents includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 2,000,000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, PEG-2M, PEG-7M, PEG-14M, PEG-45M and mixturesthereof.

F. Foaming Agent

The hair care compositions described herein can comprise a foamingagent. The hair care composition described herein may comprise fromabout from about 1% to about 10% foaming agent, alternatively from about2% to about 9% foaming agent, and alternatively from about 3% to about8% foaming agent, by weight of the hair care composition. The foamingagent can be a propellant. The hair care composition described hereinmay comprise from about from about 1% to about 10% propellant,alternatively from about 2% to about 9% propellant, and alternativelyfrom about 3% to about 8% propellant, by weight of the hair carecomposition.

The foaming agent/propellant which may be employed in the hair carecompositions described herein can be selected from the group consistingof chlorofluorocarbons (CFCs) such as dichlorodifluoromethane,1,1-dichloro-1,1,2,2-tetrafluoroethane,1-chloro-1,1-difluoro-2,2-trifluoroethane,1-chloro-1,1-difluoroethylene, monochlorodifluoromethane and mixturesthereof; hydrofluorocarbons (HFCs) such as 1,1-difluoroethane,1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and mixturesthereof; hydrofluoroolefins (HFOs) such as 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), and mixturesthereof. In addition, the foaming agent/propellants previously can bemixed with one or more hydrocarbons, chlorofluorocarbons,hydrofluorocarbons, hydrofluoroolefins, alkyl ethers, and compressedgases.

The foaming agent/propellant which may be employed in the hair carecompositions described herein can be selected from the group consistingof hydrofluorocarbons (HFCs) such as 1,1-difluoroethane,1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and mixturesthereof; hydrofluoroolefins (HFOs) such as 2,3,3,3-tetrafluoropropene(HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), and mixturesthereof. In addition, the foaming agent/propellants listed can be mixedwith one or more hydrocarbons, chlorofluorocarbons, hydrofluorocarbons,hydrofluoroolefins, alkyl ethers, and compressed gases.

Foaming agents/propellants which can be employed in the hair carecompositions described herein can be selected from the group consistingof 1,3,3,3-tetrafluoroprop-1-ene, 1,1 difluoroethane, and mixturesthereof. In addition, the foaming agent/propellants listed can be mixedwith one or more hydrocarbons, chlorofluorocarbons, hydrofluorocarbons,hydrofluoroolefins, alkyl ethers, and compressed gases.

G. Viscosity

The hair care composition may have a liquid phase viscosity of fromabout 1 centipoise (cP) to about 40,000 cP, alternatively from about1,000 to about 30,000 cP, alternatively from about 3,000 cP to about25,000 cP, alternatively from about 5,000 cP to about 20,000 cP,alternatively from about 7,000 cP to about 15,000 cP, alternatively fromabout 9,000 cP to about 12,000 cP, alternatively from about 1 cPcentipoise to about 3000 cP, alternatively from about 10 cP centipoiseto about 3000 cP, alternatively from about 20 cP to about 2000 cP,alternatively from about 500 to about 2000 cP, alternatively from about750 cP to about 1250 cP, alternatively from about 1000 to about 3000 cPmeasured at 26.5° C. as defined herein. The viscosities are measured bya Cone and Plate Controlled Stress Brookfield Rheometer R/S Plus, byBrookfield Engineering Laboratories, Stoughton, Mass. The cone used(Spindle C-75-1) has a diameter of 75 mm and 1° angle. The viscosity isdetermined using a steady state flow experiment at constant shear rateof 2 s⁻¹ at a temperature of 26.5° C. The sample size is 2.5 ml and thetotal measurement reading time is 3 minutes.

H. Perfume

The hair care composition may comprise from about 0.5% to about 7%,alternatively from about 1% to about 6%, and alternatively from about 2%to about 5% perfume, by weight of the hair care composition.

The hair care composition may have a silicone to perfume ratio of fromabout 95:5 to about 50:50, alternatively from about 90:10 to about60:40, and alternatively from about 85:15 to about 70:30.

Examples of suitable perfumes may be provided in the CTFA (Cosmetic,Toiletry and Fragrance Association) 1992 International Buyers Guide,published by CFTA Publications and OPD 1993 Chemicals Buyers Directory80th Annual Edition, published by Schnell Publishing Co. A plurality ofperfume components may be present in the hair care composition. R

I. Optional Ingredients

The hair conditioning composition described herein may optionallycomprise one or more additional components known for use in hair care orpersonal care products, provided that the additional components arephysically and chemically compatible with the essential componentsdescribed herein, or do not otherwise unduly impair product stability,aesthetics or performance Such optional ingredients are most typicallythose materials approved for use in cosmetics and that are described inreference books such as the CTFA Cosmetic Ingredient Handbook, SecondEdition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988,1992. Individual concentrations of such additional components may rangefrom about 0.001 wt % to about 10 wt % by weight of the conditioningcomposition.

Emulsifiers suitable as an optional ingredient herein include mono- anddi-glycerides, fatty alcohols, polyglycerol esters, propylene glycolesters, sorbitan esters and other emulsifiers known or otherwisecommonly used to stabilized air interfaces, as for example those usedduring preparation of aerated foodstuffs such as cakes and other bakedgoods and confectionary products, or the stabilization of cosmetics suchas hair mousses.

Further non-limiting examples of such optional ingredients includepreservatives, perfumes or fragrances, cationic polymers, viscositymodifiers, coloring agents or dyes, conditioning agents, hair bleachingagents, thickeners, moisturizers, foam boosters, additional surfactantsor nonionic cosurfactants, emollients, pharmaceutical actives, vitaminsor nutrients, sunscreens, deodorants, sensates, plant extracts,nutrients, astringents, cosmetic particles, absorbent particles,adhesive particles, hair fixatives, fibers, reactive agents, skinlightening agents, skin tanning agents, anti-dandruff agents, perfumes,exfoliating agents, acids, bases, humectants, enzymes, suspendingagents, pH modifiers, hair colorants, hair perming agents, pigmentparticles, anti-acne agents, anti-microbial agents, sunscreens, tanningagents, exfoliation particles, hair growth or restorer agents, insectrepellents, shaving lotion agents, non-volatile solvents or diluents(water-soluble and water-insoluble), co-solvents or other additionalsolvents, and similar other materials.

Anti-Dandruff Actives

The hair care compositions described herein may also contain ananti-dandruff agent. Suitable, non-limiting examples of anti-dandruffparticulates include: pyridinethione salts, selenium sulfide,particulate sulfur, and mixtures thereof. Such anti-dandruff particulateshould be physically and chemically compatible with the essentialcomponents of the composition, and should not otherwise unduly impairproduct stability, aesthetics or performance.

1. Pyridinethione Salts

Pyridinethione anti-dandruff particulates, especially1-hydroxy-2-pyridinethione salts, are one embodiment of a particulateanti-dandruff agents for use in compositions of the present invention.The concentration of pyridinethione anti-dandruff particulate typicallyranges from about 0.1% to about 10%, by weight of the composition. In anembodiment, the concentration of pyridinethione anti-dandruffparticulate ranges from about 0.1% to about 8%, and in a furtherembodiment, ranges from about 0.3% to about 5%. In an embodiment of thepresent invention, pyridinethione salts include those formed from heavymetals such as zinc, copper, tin, cadmium, magnesium, aluminum andzirconium. In an embodiment of the present invention, a pyridinethionesalts formed from a heavy metal zinc, and in a further embodiment, thezinc salt of 1-hydroxy-2-pyridinethione (known as “zinc pyridinethione”or “ZPT”), and yet a further embodiment of 1-hydroxy-2-pyridinethionesalts in platelet particle form, wherein the particles have an averagesize of up to about 20μ. In an embodiment of the present invention, theparticles have an average size up to about 5μ, and in a furtherembodiment up to about 2.5μ. Salts formed from other cations, such assodium, may also be suitable. Pyridinethione anti-dandruff agents aredescribed, for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No.3,236,733; U.S. Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat.No. 4,345,080; U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; andU.S. Pat. No. 4,470,982. It is contemplated that when ZPT is used as theanti-dandruff particulate in the compositions herein, that the growth orre-growth of hair may be stimulated or regulated, or both, or that hairloss may be reduced or inhibited, or that hair may appear thicker orfuller.

2. Other Anti-Microbial Actives

In addition to the anti-dandruff active selected from polyvalent metalsalts of pyrithione, the present invention may further comprise one ormore anti-fungal or anti-microbial actives in addition to the metalpyrithione salt actives. Suitable anti-microbial actives include coaltar, sulfur, whitfield's ointment, castellani's paint, aluminumchloride, gentian violet, octopirox (piroctone olamine), ciclopiroxolamine, undecylenic acid and it's metal salts, potassium permanganate,selenium sulphide, sodium thiosulfate, propylene glycol, oil of bitterorange, urea preparations, griseofulvin, 8-Hydroxyquinoline ciloquinol,thiobendazole, thiocarbamates, haloprogin, polyenes, hydroxypyridone,morpholine, benzylamine, allylamines (such as terbinafine), tea treeoil, clove leaf oil, coriander, palmarosa, berberine, thyme red,cinnamon oil, cinnamic aldehyde, citronellic acid, hinokitol, ichthyolpale, Sensiva SC-50, Elestab HP-100, azelaic acid, lyticase,iodopropynyl butylcarbamate (IPBC), isothiazalinones such as octylisothiazalinone and azoles, and combinations thereof. In an embodimentof the present invention, anti-microbials include itraconazole,ketoconazole, selenium sulphide and coal tar.

a. Azoles

Azole anti-microbials include imidazoles such as benzimidazole,benzothiazole, bifonazole, butaconazole nitrate, climbazole,clotrimazole, croconazole, eberconazole, econazole, elubiol,fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole,lanoconazole, metronidazole, miconazole, neticonazole, omoconazole,oxiconazole nitrate, sertaconazole, sulconazole nitrate, tioconazole,thiazole, and triazoles such as terconazole and itraconazole, andcombinations thereof. When present in the composition, the azoleanti-microbial active is included in an amount from about 0.01% to about5%. In an embodiment of the present invention, the azole anti-microbialactive is included in an amount from about 0.1% to about 3%, and in afurther embodiment, from about 0.3% to about 2%, by weight of thecomposition. In an embodiment of the present invention, the azoleanti-microbial is ketoconazole.

b. Selenium Sulfide

Selenium sulfide is a particulate anti-dandruff agent suitable for usein the anti-microbial compositions of the present invention, effectiveconcentrations of which range from about 0.1% to about 4%, by weight ofthe composition, and in an embodiment of the present invention, fromabout 0.3% to about 2.5%, and in a further embodiment from about 0.5% toabout 1.5%. Selenium sulfide is generally regarded as a compound havingone mole of selenium and two moles of sulfur, although it may also be acyclic structure that conforms to the general formula Se_(x)S_(y),wherein x+y=8. Average particle diameters for the selenium sulfide aretypically less than 15 μm, as measured by forward laser light scatteringdevice (e.g. Malvern 3600 instrument), and in an embodiment of thepresent invention, less than 10 μm. Selenium sulfide compounds aredescribed, for example, in U.S. Pat. No. 2,694,668; U.S. Pat. No.3,152,046; U.S. Pat. No. 4,089,945; and U.S. Pat. No. 4,885,107.

c. Sulfur

Sulfur may also be used as a particulate anti-microbial/anti-dandruffagent in the anti-microbial compositions of the present invention.Effective concentrations of the particulate sulfur are typically fromabout 1% to about 4%, by weight of the composition, and in an embodimentof the present invention from about 2% to about 4%.

d. Keratolytic Agents

The present invention may further comprise one or more keratolyticagents such as Salicylic Acid.

e. Additional Anti-Microbial Actives

Additional anti-microbial actives of the present invention may includeextracts of melaleuca (tea tree) and charcoal. The present invention mayalso comprise combinations of anti-microbial actives. Such combinationsmay include octopirox and zinc pyrithione combinations, pine tar andsulfur combinations, salicylic acid and zinc pyrithione combinations,octopirox and climbasole combinations, and salicylic acid and octopiroxcombinations, zinc pyrithione and climbasole and mixtures thereof. Theseactives, when used herein, are used at levels of from about 1% to about4%, and in an embodiment of the present invention, from about 2% toabout 4%.

In an embodiment, the composition comprises an effective amount of azinc-containing layered material. In an embodiment, the compositioncomprises from about 0.001% to about 10%, or from about 0.01% to about7%, or from about 0.1% to about 5% of a zinc-containing layeredmaterial, by total weight of the composition.

Zinc-containing layered materials may be those with crystal growthprimarily occurring in two dimensions. It is conventional to describelayer structures as not only those in which all the atoms areincorporated in well-defined layers, but also those in which there areions or molecules between the layers, called gallery ions (A. F. Wells“Structural Inorganic Chemistry” Clarendon Press, 1975). Zinc-containinglayered materials (ZLMs) may have zinc incorporated in the layers and/orbe components of the gallery ions. The following classes of ZLMsrepresent relatively common examples of the general category and are notintended to be limiting as to the broader scope of materials which fitthis definition.

Many ZLMs occur naturally as minerals. In an embodiment, the ZLM isselected from the group consisting of: hydrozincite (zinc carbonatehydroxide), basic zinc carbonate, aurichalcite (zinc copper carbonatehydroxide), rosasite (copper zinc carbonate hydroxide), and mixturesthereof. Related minerals that are zinc-containing may also be includedin the composition. Natural ZLMs can also occur wherein anionic layerspecies such as clay-type minerals (e.g., phyllosilicates) containion-exchanged zinc gallery ions. All of these natural materials can alsobe obtained synthetically or formed in situ in a composition or during aproduction process.

Another common class of ZLMs, which are often, but not always,synthetic, is layered double hydroxides. In an embodiment, the ZLM is alayered double hydroxide conforming to the formula [M²⁺ _(1-x)M³⁺_(x)(OH)₂]^(x+) A^(m−) _(x/m).nH₂O wherein some or all of the divalentions (M²⁺) are zinc ions (Crepaldi, E L, Pava, PC, Tronto, J, Valim, J BJ. Colloid Interfac. Sci. 2002, 248, 429-42).

Yet another class of ZLMs can be prepared called hydroxy double salts(Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg. Chem.1999, 38, 4211-6). In an embodiment, the ZLM is a hydroxy double saltconforming to the formula [M²⁺ _(1-x)M²⁺ _(1-x)(OH)_(3(1-y))]⁺ A^(n−)_((1=3y)/n).nH₂O where the two metal ions (M²⁺) may be the same ordifferent. If they are the same and represented by zinc, the formulasimplifies to [Zn_(1+x)(OH)₂]^(2x+)2x A⁻.nH₂O. This latter formularepresents (where x=0.4) materials such as zinc hydroxychloride and zinchydroxynitrate. In an embodiment, the ZLM is zinc hydroxychloride and/orzinc hydroxynitrate. These are related to hydrozincite as well wherein adivalent anion replace the monovalent anion. These materials can also beformed in situ in a composition or in or during a production process.

In an embodiment, the composition comprises basic zinc carbonate.Commercially available sources of basic zinc carbonate include ZincCarbonate Basic (Cater Chemicals: Bensenville, Ill., USA), ZincCarbonate (Shepherd Chemicals: Norwood, Ohio, USA), Zinc Carbonate (CPSUnion Corp.: New York, N.Y., USA), Zinc Carbonate (Elementis Pigments:Durham, UK), and Zinc Carbonate AC (Bruggemann Chemical: Newtown Square,Pa., USA). Basic zinc carbonate, which also may be referred tocommercially as “Zinc Carbonate” or “Zinc Carbonate Basic” or “ZincHydroxy Carbonate”, is a synthetic version consisting of materialssimilar to naturally occurring hydrozincite. The idealized stoichiometryis represented by Zn₅(OH)₆(CO₃)₂ but the actual stoichiometric ratioscan vary slightly and other impurities may be incorporated in thecrystal lattice.

In embodiments having a zinc-containing layered material and apyrithione or polyvalent metal salt of pyrithione, the ratio ofzinc-containing layered material to pyrithione or a polyvalent metalsalt of pyrithione is from about 5:100 to about 10:1, or from about 2:10to about 5:1, or from about 1:2 to about 3:1.

Method of Treating Hair

The method of treating the hair described herein can comprise (1)providing a hair care composition, as described herein, (2) dispensingthe hair care composition as a liquid form or a foam form using anaerosol foam dispenser; (3) applying the composition to the hair; and(4) rinsing the composition from the hair. The hair care composition canform a stable dosage of foam. A dosage of foam is stable when itsubstantially sustains its volume from the time of dispensing to itsapplication onto the hair.

The container can be filled with the hair care composition using astandard process known in the art. The container can be shaken tohomogenize the composition prior to dispensing. For example, thecontainer can be shaken between 1 to 10 times either immediately beforedispensing or up to 24 hr before dispensing.

Aerosol Foam Dispenser

The hair care compositions described herein can be dispensed via andaerosol foam dispenser. The aerosol foam dispenser may comprise areservoir for holding the concentrated hair treatment composition. Thereservoir may be made out of any suitable material selected from thegroup consisting of plastic, metal, alloy, laminate, and combinationsthereof. In an embodiment, the reservoir may be for one-time use. In anembodiment, the reservoir may be removable from the aerosol foamdispenser. Alternatively, the reservoir may be integrated with theaerosol foam dispenser. In an embodiment, there may be two or morereservoirs.

The reservoir may be comprised of a material selected from the groupconsisting of rigid materials, flexible materials, and combinationsthereof. The reservoir may be comprised of a rigid material if it doesnot collapse under external atmospheric pressure when it is subject toan interior partial vacuum.

The aerosol foam dispenser may comprise a dip-tube to enable uprightdispensing.

The aerosol foam dispenser may be of the bag on valve type wherein thecontainer comprises an inner bag and an outer container, which enclosesthe inner bag, while the inner bag has a valve mechanism attached whichis movable between an open position and a closed position. The outercontainer may be formed from metal or plastic or the like, and any ofthe foaming agents described herein can be filled in a space between theouter container and the inner bag (in this case the foaming agents wouldbe known as propellants to one skilled in the art). The inner bag may beflexible, and can be made from a single material or from a compositematerial including plastic, which may comprise at least a polymericlayer and a layer which acts as a gas barrier, e.g., made from metal,such as Aluminum. The inner material of the bag may be inert to thecontents of the composition, and the inner material may also beimpenetrable by the contents of the composition in the bag. The innerbag may comprise a layer of a material which is essentially impermeableto the propellant inside of the bag. The inner bag may comprise a layerof a material which is essentially impermeable to the propellant outsideof the bag which generally is not intended to be mixed with thecomposition in the inner bag during storage.

The foam can have a dosage weight of from about 1 g to about 5 g whendispensed from the aerosol foam dispenser. The foam can also have adosage weight of from about 1 g to about 7 g when dispensed from theaerosol foam dispenser, alternatively from about 2 g to about 6 g,alternatively from about 2.5 g to about 5 g, and alternatively fromabout 3 g to about 4.5 g. The dosage may be obtained via a singlesqueeze or actuation of the aerosol foam dispenser, but may beaccomplished via two or more squeezes or actuations of the aerosol foamdispenser.

The hair care compositions as exemplified herein can be delivered asfoams using the following aerosol package: an aluminum can with heightof 190 mm and diameter of 53 mm with overflow capacity of 330 mL,supplied by CCL container equipped with (a) a Cozy-Foam one-pieceactuator, supplied by Lindal; the actuator can be designed to fit a malestem and can include a nozzle channel, wherein the nozzle channel endsin a section with an inner diameter of 0.80 mm having a direction of125° in relation to the long axis of the container leading to a nozzlehaving a diameter of 5.8 mm; (b) a valve with a 0.080 inches valvehousing orifice and 2×0.040 inch stem orifice, supplied by Aptar; and(c) a dip tube having an inner diameter of 0.025 inches and a length of190 mm

EXAMPLES & DATA

The following examples and data illustrate the formulations and dosagesof foam described herein. The exemplified compositions may be preparedby conventional formulation and mixing techniques. It will beappreciated that other modifications of the formulations and dosages offoam described herein within the skill of those in the shampooformulation art can be undertaken without departing from the spirit andscope of the formulations and dosages of foam described herein. Allparts, percentages, and ratios herein are by weight unless otherwisespecified. Some components may come from suppliers as dilute solutions.The amount stated reflects the weight percent of the active material,unless otherwise specified.

Data Consumer Test Methodology

A questionnaire was established with a scale from 0-10 (0 would notprovide perceived attribute (conditioning) to 10 would provide perceivedattribute (conditioning). 20 panelists were evaluated every foam productindependently. Foam was dosed at 5 g in a small weigh boat. The panelistrated the foam from 0-10 as mentioned above. Consumer data was averagedand evaluated at the 90% confidence interval. Data is identified inTable 1 below.

TABLE 1 Test Results GU (Avg. gloss Mean Conditioning units +/− consumer(statistical Standard response grouping at Deviation) n = 3(Conditioning) 90% confidence) Ex. 1  14 (+/−4.9) 6.7 *** Ex. 4 6.1(+/−1.9)  7.0 *** Ex. 2  2.8 (+/−0.32) 4.3 * Ex. 3 2.8 (+/−0.25 4.0 **** represents significantly difference at 90% confidence for moreperceived conditioning from the dosage of foam

TABLE 2 Tested Compositions Tested Compositions Ex. 1 Ex. 2 Ex. 3 Ex. 4Sodium Laureth Sulfate (SLE1S) (1) 0 0 23.5 23.5 Sodium Undecyl Sulfate(2) 24 24 0 0 Lauramidopropyl Betaine (3) 6 6 0 0 Dipropylene Glycol (4)4 4 0 0 Cocamidopropyl Betaine (5) 0 0 2 2 Glycol Distearate (6) 0 0 1.51.5 Octopirox (7) 0 0 0 0 Zinc Pyrithione (8) 0 0 1.5 1.5 Zinc Carbonate(9) 0 0 1.61 1.61 Fragrance (10) 2.4 2.4 1.7 1.7 GuarHyrdroxypropyltrimonium 0.4 0.4 0.4 0.4 Chloride (LMW) (11) DimethiconeDM5500 (12) 0 0 1 1 Hydrochloric acid (13) 0 0 QS QS Preservative (14)0.0033 0.0033 0.05 0.05 Sodium Xylene Sulfonate (15) 0 0 2.5 2.5 SodiumChloride (16) 1 1 0 0 Citric Acid (17) 0.4 0.4 0 0 Sodium Benzoate (18)0 0 0.15 0.15 Water and Minors (QS to 100%) (19) QS QS QS QS BlowingAgent A46 (Isobutane and 0 6 4 0 Propane) (20) Blowing Agent HF0 (Trans5.5 0 0 5 1,3,3,3 Tetrafluroprop-1-ene) (21) (1) Sodium Laureth-1Sulfate from the Stepan Company (2) Sodium Undecyl Sulfate (C11, Isachem123S) at 70% active, supplier: P&G (3) LAPB (Mackam DAB), at 35% activelevel, supplier: Rhodia (4) Dipropylene Glycol from Dow Chemical (5)Amphosol HCA from Stepan Company (6) Glycol Distearate from GolschmidtChemical Company (7) Octopirox from Clariant (8) U2 ZPT from Lonza (9)Zinc Carbonate from Bruggeman Group (10) Fragrance from P&G (11) JaguarC500 from Solvay with a M. Wt of 500,000 g/mol and charge density of 0.8meq/g (12) Dimethicone DM5500, Wacker Silicone (13) Hydrochloric acidfrom Mallinckrodt Baker Inc. (14) Preservative Kathon CG from Akzo Nobel(15) Sodium Xylene Sulfonate from Stepan Company (16) Sodium ChlorideUSP (food grade) Supplier Morton (17) Citric Acid from Cargill Inc. (18)Sodium Benzoate from Kalama Chemical (19) Water from Misty MountainSpring Water (20) Blowing Agent A46 (Isobutane and Propane) DiversifiedCpc International (Channahon US) (21) Blowing Agent HF0 (Trans 1,3,3,3Tetrafluroprop 1 ene) from Honey Well

TABLE 2 Additional Example Compositions Additional Examples Ex. 5 Ex. 6Sodium Laureth Sulfate (SLE1S) (1) 23.5 24 Sodium Undecyl Sulfate (2) 00 Lauramidopropyl Betaine (3) 0 0 Dipropylene Glycol (4) 0 0Cocamidopropyl Betaine (5) 0 0 Glycol Distearate (6) 1.5 1.5 Octopirox(7) 2 1 Zinc Pyrithione (8) 1.5 1 Zinc Carbonate (9) 1.61 1.61 Fragrance(10) 1.7 2 Guar Hyrdroxypropyltrimonium 0.66 0 Chloride (LMW) (11)Dimethicone DM5500 (12) 1 0 Hydrochloric acid (13) QS QS Preservative(14) 0.05 0.0033 Sodium Xylene Sulfonate (15) 2.5 3 Sodium Chloride (16)0 0 Citric Acid (17) 0 0 Sodium Benzoate (18) 0.15 0.15 Water and MinorsQS QS (QS to 100%) (19) Blowing Agent A46 (Isobutane and 0 0 Propane)(20) Blowing Agent HF0 (Trans 5.5 5.5 1,3,3,3 Tetrafluroprop-1-ene) (21)(1) Sodium Laureth-1 Sulfate from the Stepan Company (2) Sodium UndecylSulfate (C11, Isachem 123S) at 70% active, supplier: P&G (3) LAPB(Mackam DAB), at 35% active level, supplier: Rhodia (4) DipropyleneGlycol from Dow Chemical (5) Amphosol HCA from Stepan Company (6) GlycolDistearate from Golschmidt Chemical Company (7) Octopirox from Clariant(8) U2 ZPT from Lonza (9) Zinc Carbonate from Bruggeman Group (10)Fragrance from P&G (11) Jaguar C500 from Solvay with a M. Wt of 500,000g/mol and charge density of 0.8 meq/g (12) Dimethicone DM5500, WackerSilicone (13) Hydrochloric acid from Mallinckrodt Baker Inc. (14)Preservative Kathon CG from Akzo Nobel (15) Sodium Xylene Sulfonate fromStepan Company (16) Sodium Chloride USP (food grade) Supplier Morton(17) Citric Acid from Cargill Inc. (18) Sodium Benzoate from KalamaChemical (19) Water from Misty Mountain Spring Water (20) Blowing AgentA46 (Isobutane and Propane) Diversified Cpc International (Channahon US)(21) Blowing Agent HF0 (Trans 1,3,3,3 Tetrafluroprop 1 ene) from HoneyWell

Test Methods Gloss Unit (GU)

The shine/gloss of foam is measured by utilizing a Micro-Tri Gloss metersupplied by BYK-Gardner, USA. Foam is dispensed into a sample holderknown as “round dish-G.” The gloss meter is set upon the sample holdercontaining the foam and the operate button is applied within 10 secondsof dispensing and preparing the foam in the sample holder. A 60 degreemeasurement is made. The measurements provided by the Micro-Tri Glossmeter have the unit “GU” which stands for “gloss units.” The higher theGU measurement, the glossier the foam is, and the more likely a consumeris to attribute hair conditioner benefits to the foam.

Foam Density & Foam Volume

Foam density is measured by placing a 100 ml beaker onto a mass balance,tarring the mass of the beaker and then dispensing product from theaerosol container into the 100 ml beaker until the volume of the foam isabove the rim of the vessel. The foam is made level with the top of thebeaker by scraping a spatula across it within 10 seconds of dispensingthe foam above the rim of the vessel. The resulting mass of the 100 mlof foam is then divided by the volume (100) to determine the foamdensity in units of g/ml.

Foam volume is measured by placing a weigh boat onto a mass balance,tarring the mass of the weigh boat and then dispensing the desiredamount of product from the aerosol container. The grams of foamdispensed is determined and then divided by the density of foam asdetermined from the Foam Density methodology to reach a volume of foamin ml or cm3.

Viscosity Cone/Plate Viscosity Measurement

The viscosities of formulations are measured by a Cone/Plate ControlledStress Brookfield Rheometer R/S Plus, by Brookfield EngineeringLaboratories, Stoughton, Mass. The cone used (Spindle C-75-1) has adiameter of 75 mm and 1° angle. The viscosity is determined using asteady state flow experiment at constant shear rate of 2 s⁻¹ and attemperature of 26.5° C. The sample size is 2.5 ml and the totalmeasurement reading time is 3 minutes.

Foam Rheology Method (Yield Point)

Foam shampoo is applied to the AR1000 rheometer for foam oscillationstress sweep. 60 mm smooth acrylic plate is utilized for shear stressmeasurement. Measurement is made at 25 C. The plate head is lowered to1200 microns and excess foam is removed with a spatula so that drag doesnot occur during measurement. The measurement gap height is then lowered1000 microns. Sweep occurs from 0.1 to 400 Pa. Data is analyzed via TARheology Advantage Data Analysis software. Yield point is determined atthe point at which the oscillatory shear stress begins to deviate fromits tangent. The yield point measurements are reported in Pa units.

Kruss Lather Analyzer (Bubble Size)

The commercially available Kruss lather analyzer DFA100, supplied fromKruss, is used to analyze the foam shampoo for the initial Sauter meanradius R₃₂ (bubble size). Shampoo foam is dispensed into the CY4571column containing a prism. An internal stopper is placed into the columnapproximately 100 ml from the top of the chamber. The camera height isset to 244 mm and camera position is placed in the 3 slot. Structurefoaming is captured at 2 frames per second for 120 seconds. Dataanalysis is performed on the Kruss Advance 1.5.1.0 software applicationversion.

Embodiments

-   -   A. A dosage of foam comprising:        -   a. from about 5 cm³ to about 70 cm³ of the foam;            -   wherein the foam comprises:            -   i. from about 0.5 g to about 4 g of a detersive                surfactant by weight of the foam;            -   ii. from about 0.001 g to about 4 g propellant by weight                of the foam, wherein the propellant is selected from the                group consisting of hydrofluorocarbons (HFCs),                hydrofluoroolefins (HFOs), and mixtures thereof;            -   iii. a foam density of from about 0.05 g/cm³ to about                0.35 g/cm³;            -   iv. a bubble size distribution comprising an R₃₂ of from                about 5 μm to about 100 μm; and            -   v. a gloss unit measurement of from about 4 GU to about                40 GU.    -   B. The dosage of foam of paragraph A, wherein the propellant is        selected from the group consisting of        1,3,3,3-tetrafluoroprop-1-ene, 1,1 difluoroethane, and mixtures        thereof.    -   C. The dosage of foam of paragraphs A or B, wherein the gloss        unit measurement is from about 5 GU to about 30 GU.    -   D. The dosage of foam of any of paragraphs A-C, wherein the        gloss unit measurement is from about 5 GU to about 20 GU.    -   E. The dosage of foam of any of paragraphs A-D, wherein the        gloss unit measurement is from about 5 GU to about 15 GU.    -   F. The dosage of foam of any of paragraphs A-E, wherein the        bubble size distribution comprises an R₃₂ of from about 10 μm to        about 60 μm.    -   G. The dosage of foam of any of paragraphs A-F, wherein the        bubble size distribution comprises an R₃₂ of from about 20 μm to        about 50 μm.    -   H. The dosage of foam of any of paragraphs A-G, wherein the        yield point is from about 15 Pa to about 100 Pa.    -   I. The dosage of foam of any of paragraphs A-H, wherein the        volume of the dosage of foam is from about 10 g/cm³ to about 70        g/cm³.    -   J. The dosage of foam of any of paragraphs A-I, wherein the        volume of the dosage of foam is from about 20 g/cm³ to about 70        g/cm³.    -   K. The dosage of foam of any of paragraphs A-J, wherein the foam        density is from about 0.08 g/cm³ to about 0.25 g/cm³.    -   L. The dosage of foam of any of paragraphs A-K, wherein the        detersive surfactant is an anionic surfactant.    -   M. The dosage of foam of any of paragraphs A-L, wherein the        dosage of foam further comprises from about 0.0035 g to about        0.7 g of an anti-dandruff agent by weight of the foam.    -   N. The dosage of foam of paragraph M, wherein the anti-dandruff        agent is selected from the group consisting of octopirox, zinc        pyrithione, and mixtures thereof.    -   O. The dosage of foam of any of paragraphs A-N, wherein the        propellant is 1,3,3,3 tetrafluroprop-1-ene.    -   P. A dosage of foam comprising:        -   a. from about 5 cm³ to about 70 cm³ of the foam;        -   wherein the foam comprises:            -   i. from about 0.5 g to about 4 g of a detersive                surfactant by weight of the foam;            -   ii. from about 0.001 g to about 4 g propellant by weight                of the foam, wherein the propellant is selected from the                group consisting of hydrofluorocarbons (HFCs),                hydrofluoroolefins (HFOs), and mixtures thereof;            -   iii. a foam density of from about 0.05 g/cm³ to about                0.35 g/cm³;            -   iv. from about 0.00005 g to about 0.25 g of a cationic                deposition polymer by weight of the foam;            -   v. a bubble size distribution comprising an R₃₂ of from                about 5 μm to about 100 μm; and            -   vi. a gloss unit measurement of from about 4 to about 40                GU.    -   Q. The dosage of foam of paragraph P, wherein the gloss unit        measurement is from about 5 GU to about 30 GU.    -   R. The dosage of foam of paragraphs P or Q, wherein the gloss        unit measurement is from about 5 GU to about 20 GU.    -   S. The dosage of foam of any of paragraphs P-R, wherein the        gloss unit measurement is from about 5 GU to about 15 GU.    -   T. The dosage of foam of any of paragraphs P-S, wherein the        propellant is selected from the group consisting of        1,3,3,3-tetrafluoroprop-1-ene, 1,1 difluoroethane, and mixtures        thereof.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is: 1) A dosage of foam comprising: a. from about 5 cm³to about 70 cm³ of the foam; wherein the foam comprises: i. from about0.5 g to about 4 g of a detersive surfactant by weight of the foam; ii.from about 0.001 g to about 4 g propellant by weight of the foam,wherein the propellant is selected from the group consisting ofhydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and mixturesthereof; iii. a foam density of from about 0.05 g/cm³ to about 0.35g/cm³; iv. a bubble size distribution comprising an R₃₂ of from about 5μm to about 100 μm; and v. a gloss unit measurement of from about 4 GUto about 40 GU. 2) The dosage of foam of claim 1, wherein the propellantis selected from the group consisting of 1,3,3,3-tetrafluoroprop-1-ene,1,1 difluoroethane, and mixtures thereof. 3) The dosage of foam of claim1, wherein the gloss unit measurement is from about 5 GU to about 30 GU.4) The dosage of foam of claim 1, wherein the gloss unit measurement isfrom about 5 GU to about 20 GU. 5) The dosage of foam of claim 1,wherein the gloss unit measurement is from about 5 GU to about 15 GU. 6)The dosage of foam of claim 1, wherein the bubble size distributioncomprises an R₃₂ of from about 10 μm to about 60 μm. 7) The dosage offoam of claim 1, wherein the bubble size distribution comprises an R₃₂of from about 20 μm to about 50 μm. 8) The dosage of foam of claim 1,wherein the yield point is from about 15 Pa to about 100 Pa. 9) Thedosage of foam of claim 1, wherein the volume of the dosage of foam isfrom about 10 g/cm³ to about 70 g/cm³. 10) The dosage of foam of claim1, wherein the volume of the dosage of foam is from about 20 g/cm³ toabout 70 g/cm³. 11) The dosage of foam of claim 1, wherein the foamdensity is from about 0.08 g/cm³ to about 0.25 g/cm³. 12) The dosage offoam of claim 1, wherein the detersive surfactant is an anionicsurfactant. 13) The dosage of foam of claim 1, wherein the dosage offoam further comprises from about 0.0035 g to about 0.7 g of ananti-dandruff agent by weight of the foam. 14) The dosage of foam ofclaim 13, wherein the anti-dandruff agent is selected from the groupconsisting of octopirox, zinc pyrithione, and mixtures thereof. 15) Thedosage of foam of claim 1, wherein the propellant is 1,3,3,3tetrafluroprop-1-ene. 16) A dosage of foam comprising: a. from about 5cm³ to about 70 cm³ of the foam; wherein the foam comprises: i. fromabout 0.5 g to about 4 g of a detersive surfactant by weight of thefoam; ii. from about 0.001 g to about 4 g propellant by weight of thefoam, wherein the propellant is selected from the group consisting ofhydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and mixturesthereof; iii. a foam density of from about 0.05 g/cm³ to about 0.35g/cm³; iv. from about 0.00005 g to about 0.25 g of a cationic depositionpolymer by weight of the foam; v. a bubble size distribution comprisingan R₃₂ of from about 5 μm to about 100 μm; and vi. a gloss unitmeasurement of from about 4 to about 40 GU. 17) The dosage of foam ofclaim 16, wherein the gloss unit measurement is from about 5 GU to about30 GU. 18) The dosage of foam of claim 16, wherein the gloss unitmeasurement is from about 5 GU to about 20 GU. 19) The dosage of foam ofclaim 16, wherein the gloss unit measurement is from about 5 GU to about15 GU. 20) The dosage of foam of claim 16, wherein the propellant isselected from the group consisting of 1,3,3,3-tetrafluoroprop-1-ene, 1,1difluoroethane, and mixtures thereof.